Computational and Experimental Investigations of The Structural Computational and Experimental Investigations of The Structural Selenide, Silver Sulfide, and Nickel Sulfide Nanoparticles

COMPUTATIONAL AND EXPERIMENTAL INVESTIGATIONS OF THE STRUCTURAL
PROPERTIES, ELECTRONIC PROPERTIES, AND APPLICATIONS OF SILVER, GOLD, MERCURY

SELENIDE, SILVER SULFIDE, AND NICKEL SULFIDE NANOPARTICLES
by
Jennifer Yukna
B.S., Southern Illinois University, 2001
A Dissertation
Submitted in Partial Fulfillment of the Requirements for the
Doctor of Philosophy
Department of Chemistry and Biochemistry

Southern Illinois University Carbondale
August 2007
UMI Number: 3278121
Copyright 2007 by
Yukna, Jennifer
All rights reserved.
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Copyright by Jennifer Yukna, 2007

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DISSERTATION APPROVAL
COMPUTATIONAL AND EXPERIMENTAL INVESTIGATIONS OF THE
STRUCTURAL PROPERTIES, ELECTRONIC PROPERTIES, AND APPLICATIONS
OF SILVER, GOLD, MERCURY SELENIDE, SILVER SULFIDE, AND NICKEL
SULFIDE NANOPARTICLES
By
Jennifer Yukna
A Dissertation Submitted in Partial
Fulfillment of the Requirements
for the Degree of
Doctor of Philosophy
in the field of Chemistry
Approved by:
Lichang Wang, Chair
Shaowei Chen
Daniel Dyer
Boyd Goodson
Jarlen Don
Graduate School
June 29th, 2007
AN ABSTRACT OF THE DISSERTATION OF

Jennifer Yukna, for the Doctor of Philosophy degree in Physical Chemistry, presented on
June 29, 2007, at Southern Illinois University Carbondale.
TITLE: COMPUTATIONAL AND EXPERIMENTAL INVESTIGATIONS OF THE
STRUCTURAL PROPERTIES, ELECTRONIC PROPERTIES, AND APPLICATIONS
OF SILVER, GOLD, MERCURY SELENIDE, SILVER SULFIDE, AND NICKEL
SULFIDE NANOPARTICLES
MAJOR PROFESSOR: Dr. Lichang Wang
CO-ADVISOR: Dr. Shaowei Chen
In this dissertation, computational and experimental methods were used to
investigate the structural properties of Ag clusters, the electronic properties of Ag, Ag2S,
HgSe, and NiS clusters, the coalescence of Ag clusters, and the applications of Au
clusters. Density-functional theory calculations (DFT) and molecular dynamic
simulations (MD) were used to study the Ag clusters. UV-Vis spectroscopy,
fluorescence, and electrochemistry methods were used to study Au, Ag2S, HgSe, and NiS
clusters
The DFT studies revealed that Ag linear clusters undergo Peierls bond distortion,
that planar clusters prefer a high coordination number and triangular configurations, and
that larger three-dimensional silver clusters are fluidlike and may adapt many different
configurations. The MD study of Ag clusters revealed that nucleation is dominant for the
coalescence of systems containing eight or less Ag atoms while cluster growth is
dominant in the coalescence of the systems 14 or more Ag atoms. The removal of
excessive energy is critical for the formation of Ag clusters when the collision occurs
between two clusters smaller than six atoms. The coalescence of a Ag dimer and a Ag
atom revealed that product formation was sensitive to the incident angle and that at
certain energies all three atoms were dissociated.
The synthesis and characterization of NiS, HgSe, and Ag2S nanoparticles revealed
that the solventless, thermolytic method is the best choice for nanoparticle synthesis. The
Ag2S and NiS nanoparticles exhibited fluorescence when they were synthesized using the
solventless method. HgSe nanoparticles were also synthesized using a liquid phase
approach, fluorescence only occurred for the reaction condition of C12-HgSe (rt, 4x,
0.2x). Ag2S nanoparticles produced fluorescence if the sample was heated for at least 1.5
hours.
The blocking experiments of a modified graphite electrode were discussed. The
Au nano-islands were left intact after exposure to short wavelength light and could be
blocked in whole or partially, by the electrochemical reduction of a diazonium salt or the
self-assembly of an alkanethiol monolayer, respectively. The graphite surface could be
easily blocked using the electrochemical reduction of a diazonium salt, however, there
was evidence that this EPD monolayer had defects or pinholes present.
ii
ACKNOWLEDGMENTS
I would like to give my appreciation to my research advisors, Dr. Shaowei Chen
and Dr. Lichang Wang, for their support and guidance. I would like to thank Dr. Chen
for teaching me to never be afraid to try something new and for giving me the tools to
tackle complex problems. I would like to thank Dr. Wang for her encouragement and for
all of the wonderful talks. Both of my advisers have inspired me by their great research
capabilities and desire to accomplish great goals. These are lessons that will benefit me
for a lifetime. Thanks for all of the talks, advice, and motivation.
Thanks to Dr. Lori Vermeulen, Dr. Huvos, Dr. Ge, and Dr. Tyrrell for giving me
the opportunity to teach. Special thanks to Dr. Lori Vermeulen for by inspiring me to
pursue a teaching career and then helping me develop the skills to accomplish this dream.
She is truly an inspiration and a model for the teacher I wish to become.
I would like to extend my gratitude to my committee members Dr. Boyd
Goodson, Dr. Dan Dyer, and Dr. Jarlen Don for their constructive suggestions in my
research and help throughout my graduate studies.
I would like to thank all of my friends in the Chemistry Department: Lei Cheng,
Fengjun Deng, Li Xiao, XiaoXia Li, Tiffany Pawluk, Mark Sadek, Yiyun Yang, and Tim
Roberts for the fun times. Special thanks to all of the group members for your help
during the last few years.
Finally, I wish to acknowledge my husband, my parents, my brother, and my
sister who always stand behind me and support me. Thanks to everyone who helped
during the final days of this project. Special thanks to my husband and daughter for their
encouragement. Without my family, I could never have dreamed this big. THANKS!
iii
TABLE OF CONTENTS
CHAPTER
PAGE
ABSTRACT ....................................................................................................................i
ACKNOWLEDGMENTS ........................................................................................... iii
LIST OF TABLES ........................................................................................................ix
LIST OF EQUATIONS ............................................................................................... xii
LIST OF FIGURES .....................................................................................................xv
CHAPTERS
CHAPTER 1 Introduction............................................................................................1
Introduction...............................................................................................................1
1.1 Nanoscience Background Information ...............................................................1
1.2 Theoretical Method for Cluster Studies..............................................................3
1.2.1 Density Functional Theory..........................................................................4
1.2.1.1 Exchange and Correlation Energy .................................................8
1.2.1.2 Basis Set and Electron-Ion Interactions.......................................10
1.3 Synthesis ...........................................................................................................12
1.4 Experimental Methods for Nanoparticle characterization ................................12
1.4.1 UV-Vis.....................................................................................................12
1.4.2 Fluorescence ............................................................................................13
1.4.3 Electrochemistry ......................................................................................13
1.5 Design of this Dissertation...............................................................................13
CHAPTER 2 Computational and Experimental Details............................................15
2.1 Computational Techniques ................................................................................15
2.1.1 Density Functional Theory Calculations ..................................................15
iv
2.1.1.1 VASP ............................................................................................15

2.1.1.1.1 INCAR ...........................................................................15
2.1.1.1.2 POSCAR ........................................................................18
2.1.1.1.3 POTCAR........................................................................19
2.1.1.1.4 KPOINTS.......................................................................20
2.1.1.2 Calculated Properties ....................................................................21
2.1.1.2.1 Binding Energy ..............................................................21
2.1.1.2.2 Magnetic Moment..........................................................21
2.1.1.2.3 Homo-Lumo Energy Gap ..............................................21
2.1.1.2.4 Coordination Number ....................................................22
2.1.2 Molecular Dynamic Simulations ..............................................................22
2.1.2.1 Initial Input...................................................................................22
2.1.2.2 Potential Energy Surface..............................................................26
2.1.2.3 Least Squares Fitting....................................................................27
2.1.2.4 Program........................................................................................27
2.1.2.5 Calculated Quantities ........................................................................................28
2.2 Experimental Methods for Nanoparticle Synthesis and Characterization .........28
2.2.1 Synthesis of Nanoparticles........................................................................28
2.2.1.1 Au Nanoparticles ..........................................................................29
2.2.1.2 AgS Nanoparticles ........................................................................31
2.2.1.3 NiS Nanoparticles .........................................................................32
2.2.1.3.1 Room Temperature, Liquid Synthesis ...........................32
2.2.1.3.2 Solventless Synthesis of NiS .........................................32
2.2.1.4 HgSe Nanoparticles .....................................................................33

2.2.2 UV-Vis......................................................................................................35
2.2.3 Fluorescence ............................................................................................35
2.2.4 Electrochemistry .......................................................................................36
2.2.5 Thin Film Assemblies ...............................................................................36
2.2.5.1 Au Langmuir Blodgett Thin Films ..............................................37
2.2.5.2 Covalent Modification of Carbon Surfaces .................................37
CHAPTER 3 Structural and Electronic Properties of Silver Clusters .......................39
3.1 Motivation / Background ...................................................................................39
3.1.1 Previous Theoretical Research Related to Silver Clusters........................40
3.1.2 Previous Experimental Research Related to Silver Clusters ....................41
3.2 Results and Discussion ......................................................................................41
3.2.1 Linear Ag Clusters ....................................................................................42
3.2.2 Planar Ag Clusters ....................................................................................44
3.2.3 Three-dimensional Ag Clusters ................................................................48
3.2.4 General Discussion ...................................................................................54
3.3 Summary ............................................................................................................63
3.4 Future Research Directions................................................................................63
CHAPTER 4 Coalescence of Silver clusters .............................................................64
4.1 Motivation / Background .................................................................................64
4.1.1 Previous Theoretical Research on the Coalescence of Clusters ..............65
4.2 Potential Energy Surface Construction.............................................................66
4.2.1. Potential Energy Surface Impact on the 3-Atom System .......................71
vi
4.3 Coalescence of Silver Clusters..........................................................................76

4.3.1 Coalescence of Ag2 + Ag, Ag2 + Ag2, Ag3 + Ag3, and Ag4 + Ag4 ..........77
4.3.2 Coalescence of Ag5 + Ag5 and Ag6 + Ag6 ...............................................94
4.3.3 Coalescence of Ag7 + Ag7, Ag8 + Ag8, and Ag19 + Ag19 .......................100
4.4 Summary .........................................................................................................104
4.5 Future Research Directions.............................................................................105
CHAPTER 5 Synthesis & Characterization of HgSe, AgS, & NiS Nanoparticles..106
5.1Motivation/Background ...................................................................................106
5.2 NiS Nanoparticles ..........................................................................................109
5.2.1 Room Temperature, Liquid Phase Synthesis of NiS Nanoparticles .....109
5.2.1.1 Synthesis ...................................................................................109
5.2.1.1.1 Nanoparticle Growth Dynamic ..................................110
5.2.1.1.2 Feed Ratio of Ni(Ac)2 to C6H13SH Effect..................113
5.2.1.1.3 Feed Ratio of Ni(Ac)2 to Na2S Effect ........................113
5.2.1.1.4 Effect of the Purification Process ..............................113
5.2.1.2 UV-Vis of NiS Nanoparticles ...................................................115
5.2.1.3 Fluorescence of NiS Nanoparticles...........................................118
5.2.1.4 Electrochemistry of NiS Nanoparticles ....................................124
5.2.2 Solventless Synthesis of NiS Nanoparticles .........................................128
5.2.2.1 Optical Measurements of NiS Nanoparticles............................129
5.2.2.2 Electrochemistry of NiS Nanoparticles ....................................135
5.3 HgSe Nanoparticles ........................................................................................137
5.3.1 Synthesis of HgSe ..................................................................................138
vii
5.3.2 Optical Measurements of HgSe Nanoparticles ......................................139

5.4 Ag2S Nanoparticles...........................................................................................146
5.4.1 Synthesis of Ag2S ..................................................................................146
5.4.2 Optical Measurements of Ag2S Nanoparticles ......................................146
5.4.3 Electrochemical Measurements of Ag2S Nanoparticles ........................150
5.5 Summary ........................................................................................................153
5.6 Future Research Directions............................................................................153
CHAPTER 6 Gold Nanoparticle Based Chem- & Size- Selective Electrochemical
Sensor..............................................................................................................155
6.1 Motivation/Background ..................................................................................155
6.2 Au Nanoparticle Networking on a Graphite Surface......................................158
6.3 Blocking Effects of a Graphite/Au Nanoparticle Electrochemical Sensor.....162
6.3.1 Blocking Effects Using Method A.........................................................163
6.3.2 Blocking Efects Using Method B ..........................................................166
6.3.3 Comparison of Blocking Methods .........................................................167
6.4 Summary .........................................................................................................168
6.5 Future Directions ...........................................................................................169
Bibliography ...............................................................................................................170
APPENDICIES
Appendix A Molecular Dynamics Program ............................................................181
Appendix B Copyright Permission ..........................................................................189
VITA .........................................................................................................................190
viii
LIST OF TABLES
TABLE
PAGE
Table 3.1. The structure, coordination number (Coord #), binding energy (EB), HOMOLUMO energy gap (EG), and the magnetic moment () of linear clusters. The
inserted bond lengths are in ........................................................................44
Table 3.2. The structure, symmetry, bond length (BL ), binding energy (EB), HOMOLUMO energy gap (EG), magnetic moment (), and the coordination number
(Coord. #) of different planar clusters........................................................46
Table 3.3. The structure, symmetry, bond length (BL), binding energy (EB), HOMOLUMO energy gap (EG), magnetic moment (), and the coordination number
(Coord. #) of different three-dimensional Ag clusters................................48
Table 3.4. Binding energies, EB, of the most stable structures from different methods and
functionals...................................................................................................62
Table 4.1. Sutton-Chen potential parameters obtained from the bulk and from fitting the
parameters to DFT data ..............................................................................67
Table 4.2. Binding energies, EB (eV), for the most stable clusters containing three atoms
calculated using DFT and the SC potential with bulk parameters and cluster
parameters ...................................................................................................68
Table 4.3. Final product(s) for the silver collinear AB + C reaction as a function of initial
kinetic energy, K(t=0).................................................................................74
Table 4.4. Final product(s) for the silver AB + C reaction with 1.0 eV of initial kinetic
energy as function of angle, .....................................................................75
ix
Table 4.5. Final Product(s) for the silver AB + C reaction with 0.1 eV of initial kinetic
energy as function of angle, .....................................................................76
Table 4.6. The final product(s) as a function of incident angle (see Figure 1), initial
internal kinetic energy, KI (t=0), final internal kinetic energy, KI (f), and the
impact energy, K (t=0) for the silver AB+C reaction. The final vibrational
state is included for dimer products, when present.....................................77
Table 4.7. The final product(s) and final internal kinetic energy, KI (f), for the reaction of
Ag2 + Ag2 as a function of initial kinetic energy. NS indicates a non-reactive
scattering product, i.e., the two original dimer clusters remain intact and Ag4
indicates a coalescence product. The superscripts 1-4 identify the atoms,
initially Ag21-2 + Ag23-4 ...............................................................................87
scattering product, i.e., two original trimer clusters remain intact and Ag6
indicates a coalescence product ..................................................................90
scattering product, i.e., the two original tetramer clusters remain intact and
Ag8 indicates a coalescence product ...........................................................93
Table 4.10. The final product(s) and final internal kinetic energy, KI (f), for the reaction
of Ag5 + Ag5 as a function of initial kinetic energy. NS indicates a nonreactive scattering product, i.e., the two original pentamer clusters remain
intact and Ag10 indicates a coalescence product ......................................96
of Ag6 + Ag6 as a function of initial kinetic energy. NS indicates a nonreactive scattering product, i.e., the two original hexamer clusters remain
intact and Ag12 indicates a coalescence product. The superscripts 1-12
identify the atoms, initially Ag61-6 + Ag67-12 ............................................99
of Ag7 + Ag7 as a function of initial kinetic energy. NS indicates a nonreactive scattering product, i.e., two original trimer clusters remain intact
and Ag14 indicates a coalescence product. The superscripts 1-14 identify the
atoms, initially Ag71-7 + Ag78-14 .............................................................101
of Ag8 + Ag8 as a function of initial kinetic energy. NS indicates a nonreactive scattering product, i.e., two original trimer clusters remain intact
and Ag16 indicates a coalescence product. The superscripts 1-16 identify the
atoms, initially Ag81-8 + Ag89-16 .............................................................101
of Ag19 + Ag19 as a function of initial kinetic energy. NS indicates a nonreactive scattering product, i.e., two original Ag19 clusters remain intact and
Ag38 indicates a coalescence product.....................................................103
xi
LIST OF EQUATIONS
EQUATION
PAGE
Equation 1.1. Schrdinger Equation .............................................................................3

Equation 1.2. Full Hamiltonian.....................................................................................3
Equation 1.3. Electronic Hamiltonian...........................................................................4
Equation 1.4. Electronic Schrdinger Equation............................................................4
Equation 1.5. Electronic Probability Density ...............................................................5
Equation 1.6. Hohenberg and Kohn Electronic Hamiltonian .......................................6
Equation 1.7. Electronic Energy ...................................................................................6
Equation 1.8. Electronic Energy with Electron-Electron Repulsion ............................6
Equation 1.9. Hohenberg-Kohn Electronic Energy ......................................................7
Equation 1.10. Upper Bound Ground State Energy........................................................7
Equation 1.11. Hohenber-Kohn Functional ....................................................................7
Equation 1.12. True Kinetic Energy of a System ...........................................................8
Equation 1.13. Change in electron-electron Repulsion Energy......................................8
Equation 1.14. Charge Density Energy...........................................................................8
Equation 1.15. Exchange and Correlation Energy..........................................................8
Equation 1.16. Kohn-Sham Density Functional Theory.................................................8
Equation 1.17. Local-Density Approximation................................................................9
Equation 1.18. Partitioning of the Exchange and Correlation Energy............................9
Equation 1.19. Local Spin Density Approximation........................................................9
Equation 1.20. Generalized Gradient Approximation ..................................................10
xii
Equation 1.21. Basis Set ...............................................................................................11

Equation 2.1. Binding Energy.....................................................................................21
Equation 2.2. Magnetic Moment ................................................................................21
Equation 2.3. Newtons Equation of Motion ..............................................................22
Equation 2.4. Newtons Equation of Momentum .......................................................22
Equation 2.5. Sutton Chen Potential ...........................................................................26
Equation 2.6. Sutton Chen Pair Potential....................................................................26
Equation 2.7. Sutton Chen Electron Density ..............................................................26
Equation 2.8. Internal Kinetic Energy ........................................................................27
Equation 2.9. Fitting Method ......................................................................................27
Equation 2.10. Vibrational State...................................................................................28
Equation 2.11. Synthesis of Na2Se2 ..............................................................................29
Equation 2.12. Synthesis of Ethylbenzenediazonium Fluoroborate .............................29
Equation 2.13. Reaction Scheme for Au Nanoparticles ...............................................30
Equation 2.14. Reaction Scheme for Au Nanoparticles, continued..............................30
Equation 2.15. Covalent Attachment of an Aryl Radical to the Surface of a Carbon
Electrode ...............................................................................................38
Equation 2.16. Covalent Attachment of an Aryl Radical to the Surface of a Carbon
Electrode, continued .............................................................................38
Equation 4.1. Calculation of re and k ..........................................................................72
Equation 5.1. Anodic Dissolution of NiS Nanoparticles ..........................................125
Equation 5.2. Cathodic Dissolution of NiS Nanoparticles .......................................125
Equation 6.1. Area of Au Nanoparticles...................................................................159
xiii
Equation 6.2. Reduction of the viologen dication.....................................................160

Equation 6.3.
Reduction of the viologen diradical cation........................................160
Equation 6.4.
Surface Coverage Calculation ...........................................................160
Equation 6.5.
Kolbe Reaction ..................................................................................169
xiv
LIST OF FIGURES
FIGURE
PAGE
Figure 1.1. Schematic illustration of the energy levels as a function of Density of States
for different sized systems for semiconductor and metal ..........................2
Figure 2.1. Sample INCAR file from VASP ..............................................................17
Figure 2.2. Sample POSCAR file from VASP ...........................................................19
Figure 2.3. Sample KPOINTS file from VASP..........................................................20
Figure 2.4. Schematic representation of a single atom C colliding with dimer, AB ..23
Figure 2.5. The initial configurations of Ag cluster- cluster coalescence. (a) Two
dimers initially facing each other. (b) Two dimers initially side by side. (c)
Two dimers in a T configuration. (d) Two dimers in a diamond
configuration. (e) Two planar trimers. (f) Two linear trimers. (g) Two
tetramers initially in same plane. (h) Two tetramers initially parallel. (i)
Two pentamers initially in same plane. (j) Two pentamers initially parallel.
(k) Two hexamers initially in same plane. (l) Two hexamers initially
parallel. (m) Ag7 + Ag7. (n) Ag8 + Ag8. (o) Ag19 + Ag19....................25
Figure 2.6. Schematic of the deposition of Au nanoparticles using the Langmuir
Blodgett technique ...................................................................................37
Figure 3.1. The binding energy, EB, as a function of cluster size for the linear (),
planar (), and three-dimensional () Ag clusters...................................54
Figure 3.2. The HOMO-LUMO energy gap, EG, as a function of cluster size for the
most stable Ag linear chains ....................................................................56
xv
most stable Ag planar clusters .................................................................56
most stable Ag three-dimensional clusters ..............................................57
most stable Ag clusters regardless of dimensionality ..............................57
Figure 3.6. The magnetic moment, , as a function of cluster size for the most stable Ag
linear chains .............................................................................................58
planar clusters ..........................................................................................59
three-dimensional clusters .......................................................................59
Figure 4.1. The potential energy as a function of dimer radius from DFT calculations
() and calculations using the Sutton-Chen potential with bulk parameters
(solid line) and fitted parameters (dashed line)........................................70
Figure 4.2. The silver cluster optimized (bottom) and original bulk (top) Sutton-Chen
PES for the collinear AB + C reaction. The legend shows the potential
energy in eV. The interatomic distances rAB and rBC are given in angstroms,
...............................................................................................................71
Figure 4.3. Possible reaction pathway for the coalescence of a single atom, C, and a
dimer, AB, with vibrational frequency, ................................................72
Figure 4.4. The equilibrium bond distance () determined from the first derivative
(dotted line) of the potential energy curve (solid line) as well as force
xvi
constant () determined from the second derivative (dashed line) of the

potential energy curve. The potential energy was calculated using the
Sutton-Chen potential using bulk parameters ..........................................73
(dotted line) of the potential energy curve (solid line) as well as force
constant () determined from the second derivative (dashed line) of the
potential energy curve. The potential energy was calculated using the
Sutton-Chen potential using cluster parameters ......................................73
Figure 4.6. Potential energy, V (eV), vs. time, t (fs), for the atom-atom collision of the
three atom system, AB+C. Initial impact energy, K, is (a) 1.5 eV (b) 0.5 eV
(c) 0.1 eV. In all cases the incident angle is 0o. ......................................83
Figure 4.7. Potential energy, V (eV), vs. time, t (fs), for the coalescence of the three
atom system, AB+C. Initial impact energy, K, is (a) 2.0 eV (b) 0.5 eV (c)
0.1 eV. In all cases the incident angle is 45o...........................................85
Figure 4.8. Potential energy, V (eV), vs. time, t (fs), for the coalescence of Ag3 + Ag3.
Initial impact energy, K, is (a) 1.05 eV (b) 1.42 eV. Both cases are the
planar trimer in the same plane, as shown in Figure 1(c). .......................91
Figure 4.9. Snapshots of cluster formation at t = 40 ps from the cluster-cluster collision
of two tetramers. The initial impact kinetic energy and initial cluster
orientation is given for each.
clusters in the same plane.
PA
SP
denotes an initial orientation with the two
clusters parallel to one another ...............................................................9.4
xvii

of #Ag5 + Ag5, Ag6 + Ag6, *Ag7 + Ag7, and Ag8 + Ag8. The initial impact
kinetic energy and initial cluster orientation is given for each.
denotes a
total simulation time of 80 ps. SP denotes an initial orientation with the two
clusters in the same plane.
PA
clusters parallel to one another ................................................................97

of Ag19 + Ag19. The initial impact kinetic energy is given for each snapshot.
The incident angle is 0o for each simulation..........................................104
of Ag19 + Ag19. The incident angle is given for each snapshot. The initial
impact energy is 0.95 eV for each simulation........................................104
Figure 5.1. The UV-Vis profile of NiSC6 (rt, 3X, 0.1X). Each UV-Vis profile was taken
before the addition of Na2S and at various time intervals after the addition of
Na2S .......................................................................................................111
Figure 5.2. Variation of the UV-Vis peak intensity of the NiSC6 (rt, 3X, 0.1X) with
reaction time before and after the addition of Na2S...............................111
Figure 5.3. UV-Vis spectra of the C6-NiS particles synthesized under various conditions.
The particles were dissolved in chloroform at a concentration of 0.33
mg/mL....................................................................................................115
Figure 5.4. UV-Vis Profile of C6-NiS particles synthesized with different feed ratios of
alkanethiol. The particles were dissolved in chloroform at a concentration
of 0.33 mg/mL .......................................................................................118
xviii
Figure 5.5. Excitation and Emission Spectra of C6-NiS (rt, 2x, 0.1x) nanoparticles in
chloroform. Excitation profile was collected with emission wavelength (ex)
set according to the legend, whereas for the emission spectra, the excitation
wavelength (em) was set according to the legend. The solution
concentration was 0.033 mg/mL............................................................119
chloroform. The excitation profile was collected with emission wavelength
(ex) set according to the legend, whereas for the emission spectra, the
excitation wavelength (em) was set according to the legend. The solution
concentration was 0.033 mg/mL. The first ex was chosen as 338 nm from
the corresponding UV-Vis data. These spectra were normalized to their
respective maximum intensity. ..............................................................121
chloroform. The excitation profile was collected with emission wavelength
(ex) set to 466 nm, whereas for the emission spectra, the excitation
wavelength (em) was set to 416 nm. The solution concentration was 0.033
mg/mL. The first ex was chosen as 416 nm from the corresponding UV-Vis
data. These spectra were normalized to their respective maximum intensity.
................................................................................................................122
Figure 5.8. Emission Spectra of C6-NiS (rt, 2x, 0.4x) nanoparticles in chloroform. For
the emission spectra, the excitation wavelength (em) was set according to
the 526 nm peak from the corresponding UV-Vis Profile. The solution
concentration was 0.033 mg/mL. ..........................................................123
xix
the emission spectra, the excitation wavelength (em), 252, 294, 338, 416,
and 512 nm, was chosen from the corresponding UV-Vis Profile. The
solution concentration was 0.033 mg/mL. ............................................124
Figure 5.10. Cyclic Voltammograms of a Au electrode (0.80mm2) in 0.1M TBAP
dissolved in THF with varied potential windows. The potential sweeps were
started cathodically, and the sweep rate is 100 mV/s. ...........................126
Figure 5.11. Cyclic Voltammograms of a Au electrode (0.80mm2) in 1 mg / 1mL of C6NiS (rt, 3x, 0.1) and 0.1M TBAP dissolved in THF. The potential sweep
was started cathodically, and the sweep rate was 100 mV/s..................127
Figure 5.12. Differential Pulse Voltammograms of a Au electrode (0.80mm2) in 1 mg /
1mL of C6-NiS (rt, 3x, 0.1) and 0.1M TBAP dissolved in THF............128
1mL of C6-NiS (rt, 2x, 0.1) and 0.1M TBAP dissolved in THF............129
Figure 5.14. UV-Vis Profile C12-NiS (58/80/86/190oC, 2hrs) nanoparticles in
chloroform. The solution concentration was 0.033 mg/mL..................131
Figure 5.15. Excitation and Emission Spectra of C12-NiS (58/80/86/190oC, 2hrs)
nanoparticles in chloroform. The excitation profile was collected with
emission wavelength (ex) set to 482 nm, whereas for the emission spectra,
the excitation wavelength (em) was set to 386 nm. The solution
respective maximum intensity. ..............................................................131
xx

the excitation wavelength (em) was set to 410 nm. The solution
respective maximum intensity ...............................................................133
Figure 5.18. UV-Vis Profile C12-NiS (58/80/86/210oC, 1hr) nanoparticles in chloroform.
The solution concentration was 0.033 mg/mL.......................................134
Figure 5.19. Excitation and Emission Spectra of C12-NiS (58/80/86/210oC, 1hr)
emission wavelength (ex) set to 482 nm and 521 nm, whereas for the
emission spectra, the excitation wavelength (em) was set to 388, 370, and
442 nm. The solution concentration was 0.033 mg/mL. These spectra were
normalized to their respective maximum intensity................................134
Figure 5.20. Cyclic Voltammograms of a Au electrode (0.80mm2) in 1 mg / 1mL of C12NiS (58/80/86/190oC, 2hrs) and 0.1M TBAP dissolved in THF. The
potential sweep was started cathodically and was 100 mV/s. ...............136
Figure 5.21. Differential Pulse Voltammograms of a Au electrode (0.80mm2) in 1
mg/1mL of C12-NiS (58/80/86/190oC, 2hrs) and 0.1M TBAP dissolved in
THF. .......................................................................................................136
xxi
Figure 5.22. Cyclic Voltammograms of a Au electrode (0.80mm2) in 1 mg / 1mL of C12NiS (58/80/86/210oC, 1hr) and 0.1M TBAP dissolved in THF. The
Figure 5.23. Differential Pulse Voltammograms of a Au electrode (0.80mm2) in 1
mg/1mL of C12-NiS (58/80/86/210oC, 1hr) and 0.1M TBAP dissolved in
THF. .......................................................................................................137
Figure 5.24. UV-Vis Profile C6-HgSe (rt, 4x, 0.1x) nanoparticles in chloroform. The
vertical lines depict the peak positions as determined by the second
derivative. The solution concentration was 0.033 mg/mL....................141
Figure 5.25. Emission Spectra of C6-HgSe (rt, 4x, 0.1x) nanoparticles in chloroform.
The emission spectra were collected with an excitation wavelength (em)
was set to 300, 368, 440, 470, and 512 nm. The solution concentration was
0.033 mg/mL..........................................................................................141
Figure 5.26. UV-Vis Profile C12-HgSe (rt, 1x, 0.2x)nanoparticles in chloroform. The
derivative. The solution concentration was 0.02 mg/mL......................142
The emission spectra were collected with an excitation wavelength (em)
was set to 384 and 534 nm. The solution concentration was 0.033 mg/mL.
................................................................................................................143
derivative. The solution concentration was 0.02 mg/mL......................143
xxii
Figure 5.29. Emission Spectra of C12-HgSe (rt, 4x, 0.1x) nanoparticles in CHCl3. The
emission spectra were collected with an excitation wavelength (em) was set
to 386, 442, and 486 nm. Solution concentration was 0.02 mg/mL .....144
derivative. The solution concentration was 0.033 mg/mL....................145
Figure 5.31. Excitation and Emission Spectra of C12-HgSe (rt, 4x, 0.2x) nanoparticles in
chloroform. The excitation spectrum was collected with an emission
wavelength (ex) of 440 nm and the excitation spectrum were collected with
an emission wavelength (ex) was set to 348 nm. The solution concentration
was 0.033 mg/mL...................................................................................145
Figure 5.32. UV-Vis Profile C12-Ag2S (58/80/86/150oC, 45min) nanoparticles in
Figure 5.33. Excitation and Emission Spectra of C12-Ag2S (58/80/86/190oC, 45min)
the excitation wavelength (em) was set to 292, 331, 360, and 390 nm. The
solution concentration was 0.033 mg/mL. These spectra were normalized to
their respective maximum intensity. ......................................................148
Figure 5.34. UV-Vis Profile C12-Ag2S (58/80/86/150oC, 1.5hrs) nanoparticles in
Figure 5.35. Excitation and Emission Spectra of C12-Ag2S (58/80/86/190oC, 1.5hrs)
xxiii
emission wavelength (ex) set to 424 and 434 nm, whereas for the emission
spectra, the excitation wavelength (em) was set to 346, 366, and 356 nm.
The solution concentration was 0.033 mg/mL. These spectra were
normalized to their respective maximum intensity................................149
Figure 5.36. Cyclic Voltammograms of a Au electrode (0.80mm2) in 1 mg / 1mL of C12Ag2S (58/80/86/190oC, 45 minutes) and 0.1M TBAP dissolved in THF. The
1mL of C12-Ag2S (58/80/86/190oC, 45 min) and 0.1M TBAP dissolved in
THF ........................................................................................................152
Figure 5.38. Cyclic Voltammograms of a Au electrode (0.80mm2) in 1 mg / 1mL of C12Ag2S (58/80/86/190oC, 1.5 hrs) and 0.1M TBAP dissolved in THF. The
potential sweep was started cathodically and was 100 mV/s ................152
1mL of C12-Ag2S (58/80/86/190oC, 1.5 hrs) and 0.1M TBAP dissolved in
THF ........................................................................................................153
Figure 6.1. The removal of alkanethiol from the Au nanoparticle surface...............157
Figure 6.2. Cyclic Voltammogram of a electrode with a monolayer of Au nanoparticles
after UV and ozone molecular cleaning in 0.1 M H2SO4 dissolved in water.
The potential sweep was started cathodically and was 100 mV/s. ........159
Figure 6.3. Cyclic Voltammogram of a graphite electrode (1.2cm2) with a deposited
monolayer of Au nanoparticles with V2+ self assembled on the Au surface.
The modified electrode was analyzed in 0.1 M NH4NO3 dissolved in water.
xxiv
The potential sweep was started cathodically, and the sweep rate was varied
from 5 - 200 mV/s..................................................................................161
Figure 6.4. Surface coverage determined from the peak current and sweep rate found in
Figure 6.3. ..............................................................................................162
Figure 6.5. Schematic illustration Method A of the modification of a graphite/Au
nanoparticle electrode. The first step entails the blocking of the graphite
surface by the electrochemical reduction of a diazonium salt, which leaves
only the naked Au nanoislands exposed to the analyte. The second step
completes the blocking of the entire surface by blocking the Au nanoisland
surface by the SAM of an alkanethiol....................................................162
Figure 6.6. Schematic illustration Method B of the modification of a graphite/Au
nanoparticle electrode. The first step entails the blocking of the Au
nanoislands by the SAM of an alkanethiol, which leaves only the graphite
surface exposed to analyte. The second step completes the blocking of the
entire surface by blocking the graphite surface through the electrochemical
reduction of a diazonium salt.................................................................162
Figure 6.7. Method A: Cyclic Voltammograms of a modified graphite electrode using
Method A. The CV was analyzed with a solution of 1mM (Ferro/Ferri)CN6
and 0.1 NH4NO3 dissolved in water. The potential sweep was started
cathodically, and the sweep rate was 50 mV/s. .....................................165
Figure 6.8. Method B: Cyclic Voltammograms of a modified graphite electrode using
Method B. The CV was analyzed with a solution of 1mM (Ferro/Ferri)CN6
xxv
and 0.1 NH4NO3 dissolved in water. The potential sweep was started
cathodically, and the sweep rate was 50 mV/s. .....................................167
xxvi
CHAPTER 1
INTRODUCTION
1.1
Nanoscience Background
In the last two decades, the potential for new applications and exciting discoveries
has lead many researches to conduct work on nanosized materials, which are compounds
that are 110-7 m or smaller in size. There are some fundamental reasons why nanosized
materials have novel properties and are interesting to study: the surface area to volume
ratio and the quantum size confinement effect. As a bulk material shrinks in size the
surface area, the most reactive region due in part to dangling bonds and surface defects, is
much larger than the interior volume, hence the surface plays a larger role in determining
the reactivity and properties of the material. The quantum size confinement effect
determines the spacing of energy levels in metallic and semi-conductor systems.1-5 For
instance, as the confinement becomes smaller, i.e., the number of atoms decreases, the
spacing of the energy levels increases, as illustrated in Figure 1.1. This has a significant
impact on the band gap of semiconductor systems when the size becomes smaller than
the Bohr exciton radius.6 As a bulk semiconductor shrinks in size the band gap increases
and is highly size dependent, which in turn makes it possible to fine tune the optical
properties by controlling the particle size. Metal systems are also affected by the
quantum size confinement effect; however, it doesnt have an impact until much smaller
sizes than semiconductor systems.
Figure 1.1. Schematic illustration of the energy levels as a function of Density of States
for different sized systems for semiconductor (top panel, A) and metal (bottom panel, B).
The small arrows indicate occupation of states by electrons. Adapted with permission
from Ref 5, 1997 American Chemical Society.
Due to the aforementioned reasons, the electronic, magnetic, optical, and

chemical properties of nanoparticles are highly influenced by size and shape. Because
the geometry has a profound impact on the properties of a system there is a need to
thoroughly understand the relationship between the geometry of a cluster (used
interchangeably with nanoparticles) and their properties. This importance has led to
many experimental and theoretical studies. Also, these small clusters are promising new
materials for technological applications. For instance, the robust, discrete, and size-
dependent emission of small metal clusters7-10 indicates that these clusters are excellent
candidates as optical storage devices, optical filters, optical switches, and optical
sensors.7,8,11-17 Also, metal clusters may prove to be useful in improving magnetic
storage devices as the magnetic moments of these clusters are found to be larger than in
the corresponding bulk.18 For metallic systems, coinage metal clusters (Cu, Ag, Au) are
particularly significant because of their usages in industrial applications: catalytic
reactions, corrosion processes, and coatings.
1.2
Theoretical Methods for Cluster Studies

Blackbody radiation and the discovery of the electron in the late 18th century
inspired several generations of revolutionary ideas and discoveries among physicists that
have dramatically influenced the way chemists explore and think about molecules, atoms,
and their properties. Perhaps one of the most exciting equations derived during this time
and the basis for most modern computational theories is the non-relativistic timeindependent Schrdinger equation,
v
v
v v
v v v
v v
v v v
H i ( r1 ,r2 ,...,rM ,R1 ,R2 ,...,RN ) = Ei i ( r1 ,r2 ,...,rM ,R1 ,R2 ,...,RN )
(1.1)
where H is the Hamiltonian operator for a system of N nuclei and M electrons described
by position vectors R and r, respectively. This equation also contains the eigenfunction,
i , and the eigenvalue, Ei . Using atomic units, the Hamiltonian for N nuclei and M
electrons is defined as,
N
M
N M
N N
Z
1
1
1 M M Z Z
H = i 2
2A A + + A B
i =1 2
A=1 2 M A
i =1 A=1 riA
i =1 j >i rij
A=1 B > A RAB
(1.2)
where the electrons are represented by i and j while A and B represent the nuclei. In this
equation MA is the ratio of the mass of nucleus A to the mass of an electron and ZA and ZB
are the atomic numbers of nucleus A and B, respectively. The Laplacian operator,
2
2
2
= 2 + 2 + 2 , involves the differentiation with respect to the coordinates of the
x
y
z
2
ith electron and the Ath nucleus, indicated by i2 and 2A , respectively. The kinetic
energy of the electrons and nuclei are described by the first two terms in equation 1.2,
respectively. The third term of equation 1.2 denotes the coulomb attraction between the
electrons and the nuclei. The repulsion among electrons and among the nuclei is
represented by the fourth and fifth terms of equation 1.2.
Although the Schrdinger equation contains all information needed to describe the
motions of the electrons and nuclei, it is a rather daunting task to solve this equation for
the many-bodied system. One way to simplify this equation is to use the BornOppenheimer approximation which assumes that the electrons are moving in a field of
fixed nuclei. This is a rational treatment due to the significant difference in mass
between an electron and a nucleus. Using these approximations the Hamiltonian in
equation 1.2 becomes the electronic Hamiltonian and is written as
N
N M
N N
Z
1
1
H elec = i 2 A + = Te + V NE + Vee
i =1 2
i =1 A=1 riA
i =1 j >i rij
(1.3)
where VNE , the external potential, depends on the nuclear charges and locations and
corresponds to the second term in 1.3. The repulsion of electrons and the kinetic energy
of electrons are denoted by Vee and Te , respectively. The Schrdinger equation can then
be rewritten as the electronic Schrdinger equation
v v
v
v v
v
H i ( r1 ,r2 ,...,rM ) = Ei i ( r1 ,r2 ,...,rM
1.2.1
(1.4)
Density-Functional Theory
Although the Born-Oppenheimer Approximation simplifies the full Schrdinger

equation by providing the electronic Hamiltonian and the electronic Schrdinger
equation, finding the solution is still complicated, time-consuming, and near impossible
for a many bodied system. Wide varieties of methods have been established to tackle this
problem and can be divided into four main approaches: semiempirical, ab-initio,
molecular mechanics, and density-functional theory (DFT).
The semiempirical method abandons the use of the electronic Hamiltonian given
in equation 1.3 for a simpler Hamiltonian that is adjusted by using experimental
parameters or fitting the Hamiltonian to data from ab initio calculations.19
The molecular mechanics method is not considered a quantum-mechanical
method as it simply describes molecules by the bonds that hold the atoms together. The
energy from molecular mechanic calculations is described in terms of the force constants
for bond bending and stretching. In fact neither a Hamiltonian operator nor wave
function is used in this method.19
The DFT approach is completely different as there is not attempt to calculate the
v
wave function; instead, an electron probability density, n0 ( r ) , is calculated and used to
determine the energy of the system. The electronic wave function is related to the
electron probability density19 by
v
v v v 2 v v v
n0 ( r ) = el ( r1 ,r2 ,...,rN ) dr1dr2 ...drN
(1.5)
The electron probability density was proved to uniquely determine the ground-state
molecular energy and wave function by Pierre Hohenberg and Walter Kohn in 1964.
using reductio ad absurdum.20 The electronic Hamiltonian in equation 1.3 can be
written as follows:
N
N
N N
1
1
v
H el = i 2 ( ri ) +
i =1 2
i =1
i =1 j >i rij
(1.6)
M
Z
v
v
where the external potential, ( ri ) , is given by ( ri ) = v A . This is the potential
A=1 riA
energy arising from the interaction of an electron i with the nuclei, and this interaction
depends only on the nuclear coordinates and electron is coordinates. This potential
energy is termed the external potential because it acts on an electron i and is arising
from charges external to the electron.19,20 Hohenberg and Kohn proved that the
electron probability density determines this external potential and number of electrons,
hence the Hamiltonian and wave function are determined by the electron probability
v
v
density, i.e., n0 ( r ) 0 ( r ) H 0 0 . An important aspect is that the ground state
v
energy is a functional of n0 ( r ) . The electronic Hamiltonian given in equation 1.3 is
written as the simple sum of the kinetic energy of the electrons, the potential energy due
to the electron-nuclear attractions, and the potential energy due to the repulsion of
electrons, so we can write the purely electronic energy as
E0 = Te + V NE + Vee
(1.7)
v
v
Because n0 ( r ) determines E0, we can write E0 as a functional of n0 ( r ) , E0 = E [ n0 ] ,
which means equation 1.7 can also be written as
v
v
E0 [ n0 ] = Te [ n0 ] + V NE [ n0 ] + Vee [ n0 ] = Te [ n0 ] + Vee [ n0 ] + n0 ( r )VNe dr
(1.8)
where the nucleus-electron interaction term is written as an integral as shown as the last
v
term in equation 1.8. Hence, VNE [ n0 ] is known and we are left with Te [ n0 ] and Vee [ n0 ] to
determine and we can rewrite 1.8 as
v
v
v
v
E0 [ n0 ] = Te [ n0 ] + Vee [ n0 ] + n0 ( r )VNe dr = n0 ( r )VNe dr + F [ n0 ]
(1.9)
v
where F [ n0 ] = Te [ n0 ] + Vee [ n0 ] . Although proving that if n0 ( r ) is determined the
ground state energy and the wave function could be determined, the end result is an
equation that still contains an unknown, F [ n0 ] . Therefore, for DFT to become practical
F [ n0 ] would need to be found. A second theorem was provided in the 1964 journal
article published by Hohenberg and Kohn.20 This theorem employed the variational
theorem to calculate the upper-bound of the ground state energy,
v
v
v
v
E0 = n0 ( r )VNe dr + F [ n0 ] E = n( r )VNe dr + F [ n ]
(1.10)
As stated by Hohenberg and Kohn20 in their paper, If F [ n0 ] were a known and
sufficiently simple function of n, the problem of determining the ground state energy and
density in a given external potential would be rather easy since it requires merely the
minimization of a functional of the three-dimensional density function. So, the largest
problem lies in finding the correct functional, F [ n0 ] as it is still unknown. This problem
was tackled in a 1965 paper written by Walter Kohn and Lu J Sham21, where they
determined that for a fictitious reference system of non-interacting electrons, Vee vanishes
and F [ n0 ] reduces to
F [ n0 ] Ts [ n0 ] + Exc [ n0 ]
(1.11)
where Ts is the kinetic energy of the electrons in the fictitious non-interacting reference
system and Exc [ n0 ] is the exchange and correlation energy which accounts for the Pauli
principle, dynamical correlations due to the Coulomb repulsion, and the correction of
self-interaction. The true kinetic energy of the system can be related to a reference
kinetic energy,
T [ n0 ] T [ n0 ] Ts [ n0 ]
(1.12)
where T [ n0 ] is the difference between the true kinetic energy of the system, T [ n0 ] , and
the reference kinetic energy. Define the change in electron-electron repulsion energy as
v
v
1 n( r1 )n( r2 ) v v
Vee = Vee
dr1dr2
2
r 12
(1.13)
where the second term is the classic coulomb repulsion among electrons. Now the charge
density energy of the system can be redefined as
v
v
1 n( r1 )n( r2 ) v v
v
v
E [ n0 ] = n( r )VNe dr + Ts [ n0 ] +
dr1dr2 + T [ n0 ] + Vee [ n0 ] (1.14)
2
r 12
The exchange and correlation energy, Exc [ n0 ] , can be defined by collecting the unknown
functionals as
Exc [ n0 ] = T [ n0 ] + Vee [ n0 ]
(1.15)
Including the exchange correlation energy and the exact expression for Ts [ n0 ] , the KohnSham equation takes the final form of
v
v
1 n( r1 )n( r2 ) v v
v
v 1 N
2
E [ n0 ] = n( r )VNe dr i i +
dr1dr2 + Exc [ n0 ] (1.16)
2 i
2
r 12
By separating Ts [ n0 ] and introducing the exchange and correlation energy in 1.16,

Ts [ n0 ] can be treated exactly, which is typically a large portion of the energy. The
exchange and correlation energy is a smaller contribution to the energy, however, this
energy is not negligible so approximations for Exc [ n0 ] have to be made and will be
discussed in the next section.
1.2.1.1 Exchange and Correlation Energies
Several functionals have been proposed to treat the exchange and correlation
energy contributions. Perhaps the simplest method for approximating the exchange and
correlation energy is the local-density approximation (LDA) which sets the Exc [ n0 ] to be
dependent on a uniform electron gas which is dependent only on n0 . If n0 varies slowly
with position, then
v
v
ExcLDA [ n0 ] = n ( r ) xc ( n0 )dr
(1.17)
Although this method is simple and was widely accepted by physicists, it does not give
accurate results for molecular modeling.
Another aid for approximating the exchange and correlation energy is by writing the
exchange and correlation energy as a sum of the individual exchange energy, Ex, and
correlation energy, Ec,
Exc = Ex + Ec
(1.18)
The local spin density approximation (LSDA) was proposed by Kohn and Sham in their
original work and is a popular approximation among solid state physicists and like the
LDA it is based on the uniform electron gas model.21,22 In contrast to the LDA, where
the electrons with opposite spins paired with each other are treated the same, the LSDA
allows the spin component to be introduced,
v
v
v v
ExcLSDA n n = n ( r ) xc ( n ( r ) n ( r ) )dr
(1.19)
Although LSDA is an exact method for a uniform density, it has some significant
drawbacks. Among them, LSDA does not incorporate known inhomogeneity.
Obviously, most systems are not homogeneous; hence, this becomes a major problem
when using the LSDA. To improve the LSDA method, corrections aim to address the
problem of non-uniformity by variation of the electron density with position. This leads
to the addition of a gradient expression into equation 1.19.
v
v
v
v
v v
GGA
n n = n [ r ] xc ( n ( r ) n ( r ) ( r ) ( r ) )dr
Exc
(1.20)
The first generalized gradient approximation (GGA) for the correlation energy was
introduced in 1968 by Ma and Brueckner.22 Since that time many GGAs have been
proposed, i.e., by Langreth and Mehl; Perdew; Lee, Yang, and Parr; Perdew and Wang;
and Perdew, Burke, and Ernzerhof.22 However, some GGA focus only on the correction
of Ex or Ec. For instance, the gradient exchange functional, GGA Ex was treated in work
done by Perdew and Wang in 1986 and 1991 or the 1988 functional developed by Becke.
Some commonly used gradient corrected correlation functional, GGA Ec, are the 1986
Perdew functional, the Lee-Yang-Parr functional, or the Perdew-Burke-Ernzerhof.19,22
Conveniently, any gradient corrected exchange functional can be combined with any
gradient corrected correlation functional.
Although GGA functionals make significant improvements to the LSDA and are good
choices for computational studies, the GGA still tends to overestimate bond lengths and
binding energies.22 Hence, on going research is directed to developing more accurate
exchange and correlation functionals.
1.2.1.2 Basis Sets and Electron-Ion Interactions
10
Wave functions can be constructed using atomic orbitals, which are one-electron
spatial wave functions.22 The linear combination of basis functions is used to construct
an orbital for atoms in a given molecule. By expanding a set of orbitals in a set of known
spatial basis functions, a basis set,
v
i ( r ) = C i ( r )
(1.21)
=1
the wavefunction could be determined. However, to find all of the exact orbtials for even
a simple molecule, i.e. H2, an infinite number of terms would be needed in the expansion
given in equation 1.21; hence, for larger molecules choosing the type and number of basis
sets used in the calculation is an important consideration when balancing the accuracy
and calculation time.
The most popular basis sets used to construct orbitals can be broken up into two major
categories: Slater-type functions (STF) and Gaussian type functions (GTF). Both of
these types contain an orbital exponent which is used to determine the size of the basis
function.19,22 In terms of accuracy, it is much better to use a STF, but GTF out does STF
in terms of computational cost. This led to the addition of a contraction term to the
GTFs, which makes it easy for the GTF to assume the form of other functions, including
STFs. One simple basis set is the production of Slater-type orbital (STO) from GTFs.
For instance, one common example is the STO-3G, which is a STO produced from the
linear combination of three GTFs.
Another type of basis function used to expand the electron wave function is a
plane waves basis set; unlike GTF and STF, the functions used in a plane wave basis set
are not localized on the atoms.22 The use of plane waves is particularly successful for
periodic systems and can be used for finite systems such as molecules and clusters.
11
However, due to the concentration of electron density of the molecule, a large number of
plane-waves will be needed for convergence and accurate results, greatly increasing
computational cost. To reduce the number of plane waves needed, the core electrons,
which are mostly inert, together with the nucleus can be treated as an effective potential
felt by the valence electrons. This effective potential is called pseudo-potential, reduces
the atom to an ionic core that interacts with the valence electrons.
Pseudo-potentials were first introduced in 1934 by Fermi and mostly forgotten about until
the late 1950s.22,23 Similar to the exchange and correlation functionals, there are many
proposed pseudo-potentials. One popular type of pseudo-potential is the ultra-soft
pseudo-potential, which replaces not only the core orbitals but some of the inner valence
part of the orbital by a potential.24,25 26 This provides a further reduction in the number of
plane waves needed for DFT calculations, particularly those involving transition metals.
Another method that treats the core electrons to increase the computational cost
effectiveness of DFT calculations of heavy metals is the Projector-Augmented Wave
Method (PAW). The PAW method implements frozen wave functions for the core states
and an augmented plane wave basis set for the electronic valence functions.27 In
comparison to the ultrasoft-pseudopotentials, the PAW method is more accurate and is
the same cost effective as the pseudopotential method.
1.3
Synthesis of Metal and Semiconductor Nanoparticles
Semiconductor and metal nanoparticles can be synthesized using a variety of

liquid phase preparations28-32or gas phase preparation33. The sizes, shapes, stability,
functionality, and dispersity vary greatly amongst the different synthetic routes. A more
detailed discussion of different synthetic methods will be given in chapters 2 and 5.
12
1.4
Experimental Methods for Nanoparticle Characterization
1.4.1
UV-Vis
One of the most important properties of semiconductor nanoparticles is the

significant changes in their optical properties. Specifically, as the size of the system
decreases, their electronic excitations shift to higher energies. Therefore, the threshold
energies of semiconductor nanoparticles exhibit a blue-shift from near-infrared to the
visible region.1,5,9,10,34-44 This shift to the visible regions renders the possibility of
exploring the electronic structure of semiconductor nanoparticles as a function of
nanoparticles size with conventional UV-Vis spectroscopy.
1.4.2
Fluorescence
At room temperature, semiconductor nanoparticles have been shown to have

narrow band size-dependent luminescence. Because the luminescence is dependent upon
size and chemical environment, semiconductor nanoparticles have potential uses in light
emitting devices35-37,45,46 and biosensors.9,10,39,47 Thus, the study of a nanoparticles
photoluminescence is essential when examining newly synthesized materials.
1.4.3
Electrochemistry
The electron-transfer chemistry is another interesting property of semiconductor

nanoparticles that can be regulated as a function of size. Electrochemical studies of
semiconductor nanoparticles in solution can also reveal information about the band-gap
energy of the particles as well as the possibility of single-electron quantized charging
which is an important property for use in nanoelectronics and nanocircuitry.48-50
1.5
Design of this Dissertation
13
The work in this dissertation is directed to shed light on two areas of nanoparticle
research: computational investigations of Ag nanoparticles and experimental
investigations of Ag2S, NiS, Au, and HgSe. In the first portion, the calculated electronic
and magnetic properties of silver nanoparticles are correlated to their corresponding
geometries using Density Functional Theory calculations. In addition, the growth of
silver clusters is monitored for a bimolecular reaction as a function of kinetic energy and
cluster geometry using molecular dynamic simulations. The second portion of this paper
focuses on the actual production of metal and semiconductor nanoparticles in the liquid
phase and a solventless method as a function of reaction conditions: precursor ratios and
reaction time. Here the produced nanoparticles are examined to monitor their electronic
properties using electrochemistry, UV-visible spectroscopy, and fluorescence
spectroscopy.
14
CHAPTER 2
COMPUTATIONAL AND EXPERIMENTAL DETAILS
2.1
Computational Techniques
2.1.1
Density-Functional Theory Calculations
The Kohn-Sham Density Functional Theory Calculations were performed in the

Vienna ab-initio Simulation Package using a plane wave basis set. The cut-off energy of
the basis set is set to 300eV. The exchange and correlation energy were described with
the Perdew-Wang 91 (PW91) form of the Generalized Gradient Approximation (GGA).
The electron-ion interactions were described with the Projector-Augmented Wave
method.51 A supercell size was chosen such that the distance between neighboring
clusters, a direct result of the periodic nature of VASP, was 8 in each dimension. This
choice is sufficient to eliminate the interaction of neighboring images. Due to the large
supercell, the Brillouin zone was sampled with the point only.
2.1.1.1
VASP
VASP is a complex package that can be utilized for a wide variety of calculations,
however, there are four basic input files required for all calculations: INCAR, POSCAR,
POTCAR and KPOINTS.52
2.1.1.1.1 INCAR
INCAR is a guide file, in that it determines what calculation to perform and how
to run the calculation.52 A sample INCAR file is shown below in Figure 2.1. This file
contains a large number of parameters, which are set to a default value or changed by an
experienced operator. This file is very powerful, it can be used to better control a
15
calculation, but it is also the most prone to an operators accidental input, resulting in
errors or false results.
Each line in the INCAR file contains a flag the corresponding value of that flag.
For instance, after the user defined description of this calculation on line one, the first
flag shown in Figure 2.1 is the NWRITE flag, which determines how the much
information should be written to the output file. Other important flags used for this
project are the ENCUT, ISPIN, ICHARG, NELM, EDIFF, NSW, EDIFFG, and GGA.
ENCUT determines the cut-off energy for the plane wave basis set which has a
default value taken from POTCAR if no value is given. In this work the cut-off energy is
set at 300.00 eV, which means that all plane waves with a smaller kinetic energy than 300
eV will be included in the basis set but those with a higher kinetic energy will be omitted
in the basis set. Higher cut-off energies will give better results but the calculations will
be more time consuming.
16
System = Ag3-04091301
Startparameter for this Run:
NWRITE = 2; LPETIM=F write-flag & timer
ENCUT = 300.000
PREC = medium
ISTART =
0 job : 0-new 1-cont 2-samecut
ICHARG = 2 charge: 1-file 2-atom 10-const
ISPIN = 2 spin polarized calculation?
INIWAV =
1 electr: 0-lowe 1-rand 2-diag
NELM = 200; NELMIN= 2; NELMDL= 10 # of ELM steps
EDIFF = 0.1E-04 stopping-criterion for ELM
Ionic Relaxation
EDIFFG = -0.2E-01 stopping-criterion for IOM
NSW =
200 number of steps for IOM
NBLOCK =
1; KBLOCK = 100 inner block; outer block
IBRION = 2 ionic relax: 0-MD 1-quasi-New 2-CG
ISIF = 2
IWAVPR =
1 prediction: 0-non 1-charg 2-wave 3-comb
ISYM = 2 0-nonsym 1-usesym
LCORR =
T Harris-correction to forces
POTIM = 0.5 time-step for ion-motion
TEIN = 5000.0 initial temperature
TEBEG =
5000.0; TEEND = 5000.0 temperature during run
SMASS = -1 Nose mass-parameter (am)
GGA = 91
Electronic Relaxation 2
IALGO =
48 algorithm
LDIAG =
T sub-space diagonalisation
LREAL =
F real-space projection
LCHARG = F
LWAVE = F
DOS related values:
EMIN = 10.00; EMAX =-10.00 energy-range for DOS
ISMEAR = 0; SIGMA = 0.002 broadening in eV -4-tet -1-fermi 0-gaus
NPAR = 4
LSCALU =F
NSIM = 4
Figure 2.1. Sample INCAR File from VASP
17
The tag ISPIN designates a spin polarized calculation by setting the value to 2,
which is the value used for the study of Ag, a transition metal. The ICHARG tag
determines how the initial charge density be constructed, which can be constructed from
the initial wave functions, input from the charge density file, CHGCAR, taken from the
superposition of atomic charge densities, or from non-selfconsistent calculations. For
this study the charge density is constructed by taking the superposition of atomic charges.
NELM determines the maximum number of electronic self-consistent steps to be
performed. The default value for this tag is 40 steps, but this number can be increased,
although the calculation is unlikely to converge if it doesnt converge within 40 steps. To
specify where the global self-consistent loop will break, the EDIFF flag is set to a default
value of 10-4. The allowed error in total energy is determined by the EDIFF value. In
addition to the number of electronic steps, the number of ionic steps can be set by using
the flag NSW to set the number of ionic steps. To determine when the ionic relaxation
will break the flag EDIFFG can be set to a specific value, however for this study EDIFFG
is set to a negative value which directs the ionic loop to stop if all forces are smaller than
the absolute value of EDIFFG.
To perform a generalized gradient approximation calculation with
pseudopotentials, the tag GGA should be specified to the desired functional. For
instance, the Perdew Wang 91 gradient-corrected exchange and correlation functional is
used for this study.
2.1.1.1.2 POSCAR
The POSCAR file provides the lattice vectors and the input coordinates of the
atoms. A sample POSCAR is shown below, in Figure 2.2. The first line of the POSCAR
18
file is comment line to provide a description for the structure inputted. The second line in
the file is a universal scaling factor, which is used to scale the lattice vectors. The next
three lines are the lattice vectors of the unit cell of the system. For cluster calculation
these vectors should provide adequate vacuum space between the cluster and its
neighboring image in any direction. For this study a vacuum space of at least 8 is
chosen. Line number six in the file is the number of atoms in the system and informs
VASP how many coordinates should be submitted. The next line determines how the
positions of the atoms will be entered, either as Cartesian coordinates or direct mode. For
this study the positions of the atoms will be entered using simple Cartesian coordinates as
indicated by the Cart flag. Following the Cartesian coordinate flag the coordinates of the
atoms are listed.
Ag size 3, structure
1.0
10.2 0.00 0.00
0.00 11.2 0.00
0.00 0.00 9.08
3
Cart
0.00000 0.00000 0.00000
2.54000 0.00000 0.00000
1.58856 2.35500 0.00000
Figure 2.2. Sample POSCAR file from VASP
2.1.1.1.3 POTCAR
The POTCAR file contains the pseudopotentials for each atom entered in
POSCAR. The generation of pseudopotentials is a time consuming and tricky task,
which motivated the authors of VASP to supply a set of standard pseudopotentials, which
19
have been found to be among the best available pseudopotentials. These developed
pseudopotentials are of the ultra soft type and contain default values for cut-off energy
which can be overridden by setting a new cut-off energy within the INCAR file.
2.1.1.1.4 KPOINTS
The KPOINTS file determines how many k-points will be used to sample the
Brillouin zone. The generation of k-points can be done using several different methods
within the KPOINTS file: entering the k-points explicitly, generating strings of k-points
that connect specific points of the Brillouin zone, and the automatic generation of the kmesh. In the case of atoms and molecules the Bloch theorem does not apply, therefore,
only one k-point needs to be supplied. For this study the Monkhorst Pack is used to
generate the gamma-point. Figure 2.3, shown below, demonstrates how k-points can be
automatically generated.
K-Point Grid
0
Monkhorst Pack
111
000
Figure 2.3. Sample KPOINTS file from VASP
As before, the first line in the KPOINTS file is a comment supplied by the
operator. The second line is required to be set to zero for the complete automatic
generation of k-points. To select a generation scheme, the third line should be set to the
desired scheme; in this case the k-points are generated using the Monkhorst Pack scheme.
The fifth line subdivides the reciprocal lattice vectors, which in turn controls the number
20
of k-points generated. In this case only one k-point is generated. The last line in the file
shifts the k-mesh in relation to the origin used in the generation scheme. In this study,
the k-mesh remains centered on the Monkhorst Pack origin.
2.1.1.2 Calculated Properties
The output from the theoretical calculations will be analyzed to determine the
stability of the cluster, the electronic properties, magnetic properties, and structural
information, which will be found by calculating the binding energy, the HOMO-LUMO
energy gap, the magnetic moment, and coordination numbers and bond lengths,
respectively.
2.1.1.2.1
Binding Energy
The binding energy per atom is given by,

EB = (N * EAtom ECluster)/N,
(2.1)
where EAtom and ECluster represent the total energy of a silver atom and the silver cluster,
respectively. Both EAtom and ECluster have a unit of eV and N is defined as the number of
atoms in the cluster. Hence, the unit of EB is eV/atom. The energy of a silver atom was
found to be -0.181eV. According to this notation, the most stable cluster will have the
largest positive binding energy.
2.1.1.2.2
Magnetic Moment
The magnetic moment () is calculated by

= (mu md)/N,
(2.2)
where mu and md are the number of electrons with a up and a down spin, respectively.
The unit of the magnetic moment is B/atom
2.1.1.2.3
HOMO-LUMO Energy Gap
21
The HOMO-LUMO energy gap of the cluster, EG, is obtained by the difference
between the energies of the lowest unoccupied level and of the highest occupied level.
The HOMO-LUMO energy gap is reported in eV.
2.1.1.2.4
Coordination Number
The coordination number is found by taking the number of bonds and dividing
that by the number of atoms in the cluster.
2.1.2
Molecular Dynamic (MD) Simulations
Classical molecular dynamic simulations use Newtons equation of motion for

position, xi, yi, and zi,
p x dy
p y dz
pz
dx i
= i , i = i , i = i
dt
mi dt
mi dt
mi
(2.3)
and momentum, pxi , p yi , and pzi ,

dp xi
dt
V
V dp zi
V dp yi
,
,
,
=
=
z i
y i dt
xi dt
(2.4)
to compute the trajectory53 of all atoms of a system. This is based on the Cartesian
coordinates x, y, and z for each atom, i, where mi is the mass of the ith atom, and V is the
potential energy surface described in 2.1.2.2. The sixth order Runge-Kutta54 method is
used to integrate the equations of motion and is discussed later.
During the simulations the total energy and the total linear momentum of the system were
conserved. The stopping criterion for the coalescence studies was a distance of 10
between two nearest atoms or at the end of the set simulation time, whichever comes
first.
2.1.2.1 Initial Input
22
The coalescence of silver clusters was investigated in two different manners:

small atom coalescence and cluster coalescence. The small atom coalescence studies, as
shown in Figure 2.4, consisted of a single atom, C, colliding with a dimer, AB. Initially,
R, the distance of atom C from the center of mass of the dimer, is set to 10 which is a
sufficient distance to ensure that the single atom and the dimer are in the asymptotic
region. In addition the bond distance of AB, r, is set to 2.54 which is the equilibrium
bond distance for a silver dimer. The equilibrium bond distance of the dimer was found
by calculating the binding energy of the silver dimer as a function of bond distance using
the Sutton-Chen potential. The small atom coalescence was studied as a function of the
incident angle, , from zero to 90 degrees.
The initial kinetic energy of the system was supplied to atom C whose momentum
was directed towards the center of mass of the dimer as indicated by the arrow in Figure
2.2.1.1. The initial kinetic energy was varied from 0.02 eV to 2.0 eV.
Figure 2.4 Schematic representation of a single atom C colliding with a dimer AB. The
arrow indicates the direction of the initial momentum of atom C.
23
The coalescence of two equal sized silver clusters, i.e. Agn + Agn (n = 2 8, 19)
was also studied. The starting geometry of the colliding clusters was chosen from the
most stable DFT structures discussed in Chapter 3 and are given in Figure 2.5. Silver
clusters from two to eight atoms were collided collinearly, while the coalescence of the
19 atom clusters was studied collinearly and as a function of incident angle, as shown in
Figure 2.5. Initially, the distance between any two atoms of the colliding clusters was set
to 8 . In all studies, the initial kinetic energy, K(t=0) was given entirely to the second
cluster to collide with the first cluster. The impact kinetic energy, K(t=0) = 0.3 1.9 eV,
was distributed among the x coordinates of all atoms in the second cluster.
The simulations for the 3-atom system were performed over a 10 ps time period
by calculating the positions and momentums (trajectories) at each time step of 0.01 fs for
a total of 1,000,000 steps; hence, the total simulation time is 10 ps. For the coalescence
of two equal sized clusters the trajectories were obtained with a time step of 0.05 fs for a
total of 800,000 steps; hence, the total simulation time is 40 ps which is ample time to
monitor the product formation during coalescence. Any complex lasting longer than 10
ps for Ag2 + Ag or 40 ps for Agn + Agn with n = 2 8, 19 is considered long lived.
24
(b)
(a)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(l)
(m)
(n)
(o)
Figure 2.5. The initial configurations of Ag cluster- cluster coalescence. (a) Two dimers
initially facing each other. (b) Two dimers initially side by side. (c) Two dimers in a T
25
configuration. (d) Two dimers in a diamond configuration. (e) Two planar trimers. (f)
Two linear trimers. (g) Two tetramers initially in same plane. (h) Two tetramers
initially parallel. (i) Two pentamers initially in same plane. (j) Two pentamers initially
parallel. (k) Two hexamers initially in same plane. (l) Two hexamers initially parallel
(m) Ag7 + Ag7. (n) Ag8 + Ag8. (o) Ag19 + Ag19.
2.1.2.2 Potential Energy Surface
The coalescence studies consist of atoms that are modeled by the Sutton-Chen55
potential,
1
V = v(rij ) c i
i
2 ij
(2.5)
where the pair potential is given by,

a
v(rij ) =
r
ij
(2.6)
and the local electron density is given by,

a
i =
j rij
(2.7)
to describe the interactions among atoms in the system. In Eqs. (2.5) - (2.7), rij is the
distance between two atoms and , a, c, m, and n are parameters, which are constant for
each metal but vary for different metals. These potential parameters were obtained by
Sutton and Chen55 for different metals by fitting the bulk properties of each metal.
During the entirety of the simulations, the total energy and the total linear angular
momentum of the system were monitored for their conservation. The total energy, E, is
26
given by, E = K + V, where the kinetic energy is given by K =

i
px2,i + p 2y ,i + pz2,i
2mi
. The
internal kinetic energy, KI, was also calculated and has the form, KI = K - Ecom, where
2
Ecom =
2
pcom
2mcom
p x ,i ( t = 0 ) + p y ,i ( t = 0 ) + p x ,i ( t = 0 )
i
i
= i
2 mi
(2.8)
As defined above, the internal kinetic energy is the energy of the motion of the atoms
without the translational and rotational energy of the entire system.
2.1.2.3 Least Squares Fitting Method
The task to find new parameters for the Sutton Chen potential is accomplished
by fitting the parameters a, c, and to the findings from the DFT study of Ag clusters.
The fitting method used is a nonlinear least squares multidimensional model, the
Levenberg Marquardt54 method. This method minimizes 2, which is defined by the
following:
y v
= i i
i =1 i
(2.9)
where y is a function of a, c, and , vi is the DFT value, N is the number of data points
involved in the fit, and i is the standard deviation of each data point. In this study i is
equal to one.
2.1.2.4 Program
The software used to run the molecular dynamic simulations was partially
developed by the author. The program to steer the calculations is shown in Appendix A.
The number of time steps, time interval, kinetic energy, and cluster geometry are read by
this program from two input files.
27
2.1.2.5 Calculated Quantities
The vibrational state of products that are dimers, where present, was estimated
using the harmonic oscillator treatment, in which the vibrational state, , was calculated
by
1
Edimer = h e +
2
(2.10)
1
k
with being the reduced mass of the
where h is the Plancks constant and e =
2
dimer and k being the force constant obtained from the potential energy curve, and Edimer
is the vibrational energy of the dimer.
2.2
Experimental Methods for Nanoparticle Synthesis and Characterization
2.2.1 Synthesis of Metallic and Semiconductor Nanoparticles
Chemicals: Nickel acetate (Ni(Ac)2, Fisher ), sodium sulfide (Na2S, Fisher) silver
nitrate (AgNO3, Fisher), Hg(Ac)2, Tetra-n-octyl-ammonium bromide (TOABr, 98%,
Aldrich), n-hexanethiol (C6H13SH, 96%, ACROS), dodecanethiol (C12H25SH, Aldrich),
sodium borohydride (NaBH4, 98+%, Aldrich), 4-ethylaniline (C8H11N, 99+%, ACROS),
fluoroboric acid (HBF4, 50%, ACROS), sodium nitrite (NaNO2, ACROS),
tetrabutylammonium tetrafluoroborate (TBABF4, 99%, ACROS), 4,4thiobisbenzenethiol (TBBT, 98%, Aldrich), potassium ferrocyanide (II) trihydrate
(K4Fe(CN)6, ACROS), tetra-n-butylammonium perchlorate (TBAP, ACROS), methyl
viologen (V2+, Aldrich) sodium octanoate (Na+-OOC(CH2)10CH3, Aldrich), and
potassium ferricyanide (K3Fe(CN)6, Fisher) were used as received. Ammonium Nitrate
(NH4NO3, Fisher) was re-crystallized prior to use. All solvents were obtained from
28
typical commercial sources and used as received as well. Water was supplied by a
Barnstead Nanopure water system (18.3M).
Sodium selenide was synthesized according to a procedure given by Klayman and
coworkers.56 Briefly, 76 mmol of selenium is added to a stirring flask of 150 mL of
ethanol in an ice bath and continued to stir for 30 minutes, which produces a black
solution. Then 84 mmol of sodium borohydride is added to the black solution and slowly
turns reddish-brown. This reaction can be summarized as follows56,
2NaBH4 + 3Se + 6C2H5OH Na2Se2 + H2Se + 2B(OC2H5)3 + 6H2
(2.11)
The synthesis of ethylbenzenediazonium fluoborate, C6H5N2BF4, was described

according to the procedure by Starkey and co-workers57, shown in equation 2.12.
NH2
N2BF4
+ NaNO2 + 2HBF4
+ NaBF4 + 2H2O
(2.12)
Briefly, 0.1 mole of 4-ethylaniline was added to 44 mL of HBF4 and stirred in an
ice bath for twenty minutes. To the stirring solution, 0.1 mole of sodium nitrite in 14 mL
of water was added drop-wise. After stirring for an additional ten minutes the product
was filtered using a sintered glass filter. The solid was then rinsed with cold fluoroboric
acid, cold ethanol, and cold ether.
2.2.1.1 Au Nanoparticles
1-Hexanethiolate-protected gold (C6Au) nanoparticles were synthesized by the

Schiffrin route.58-60 This two-phase, two step method consists of metallic nuclei growth
with the simultaneous attachment of self-assembled thiol monolayers to the metal
nuclei.58 The typical reaction involves the mixing of an aqueous solution of hydrogen
29
tetrachloroaurate (1 mmole of AuCl4- in 20 mL of H2O) with tetra-n-octylammonium

bromide in toluene (2 mmoles of tetra-n-octylammonium bromide in 80 mL of toluene),
which is then stirred vigorously to allow the complete transfer of AuCl4- to the toluene
phase. After stirring for 30 minutes it is apparent that the phase transfer of AuCl4- is
complete as the toluene phase turns an orange color and the water phase is colorless.
Hence, the water phase is separated from the organic phase and discarded. To the
organic phase, 3 mmoles of Hexanethiol was added and allowed to stir for 30 minutes.
The stirring flask was then placed in an ice bath for 20 minutes prior to the slow addition
of an aqueous solution of sodium borohydride (10 mmoles of NaBH4 in 10 mL of H2O).
The toluene phase turned from orange to black after addition of the sodium borohydride
indicating the formation of Au nanoparticles. After stirring for 30 minutes at 0oC, the
solution was removed from the ice bath and allowed to stir at room temperature for 24
hours. The organic layer was then separated from the H2O layer and evaporated in a
rotary evaporator and rinsed with copious amounts of ethanol to remove excess thiol.
The dark brown precipitate was filtered from the ethanol and again washed with copious
amounts of ethanol. The monolayer protected Au clusters (MPCs) were collected by
rinsing with toluene, but are stored in the absence of solvent.
AuCl4-(aq) + N(C8H17)4 + (C6H5Me) N(C8H17)4 + AuCl4-(toluene)
(2.13)
mAuCl4-(toluene) + nC6H13SH(toluene) + 3me-

4mCl-(aq) + (Aum)( C6H13SH)n(toluene)
(2.14)
The synthesis of Au nanoparticles is summarized in equations 2.13 and 2.14. To

narrow the size dispersity, a fractionation scheme using a solvent and non-solvent
mixture (e.g. toluene and ethanol) was used to narrow the size dispersity. Thermal
30
annealing, the refluxing of the Au nanoparticles in toluene for eight hours, results in a
mostly spherical shape and mono-disperse size with a final average particle core diameter
of 2.0 nm.
2.2.1.2 Ag2S Nanoparticles
Larsen and co-workers demonstrated that size- and shape-monodisperse CuS

nanorods could be synthesized using a solventless method.61 The main advantage of
using a solventless method to synthesis semiconductor nanoparticles is the absence of
interparticle collisions which are typical in liquid phase synthesis as both molecular and
nanoparticle diffusion occurs very fast in solvent. Hence, in the solventless method,
nanoparticles growth proceeds primarily by monomer addition to the particle surface.61
This procedure has been repeated here for the solventless synthesis of Ag2S
nanoparticles.
In the typical reaction, fifty-eight mmoles of AgNO3 is dissolved in 36 mL of
water under vigorous stirring, which produces a greenish-blue solution. Then, 24.5 mL
of chloroform is added to the stirring solution. To this solution, 80 mmoles of Na+OOC(CH2)10CH3, a phase transfer catalyst, is added which turns the chloroform phase
green. The solution is then stirred for 30 minutes. Then the chloroform phase is
separated and collected from the water phase. Eighty-six mmoles of dodecanethiol is
then added to the chloroform phase and stirred for 30 minutes at room temperature. The
chloroform is then removed and the dry nanoparticles are then heated at various
temperatures for different amounts of time. The Ag2S nanoparticles produced with this
procedure are denoted as C12-AgS (58, 80, 86, 190oC, 45), to denote the starting amounts
31
of AgNO3 (58 mmoles) to Na+-OOC(CH2)10CH3 (80 mmoles), and C12H25SH (86

mmoles), which is heated at 190oC for 45 minutes
2.2.1.3 NiS Nanoparticles
The NiS nanoparticles were synthesized using two different methods. The first
method takes place at room temperature throughout the entire synthesis. The second
synthetic route, the solventless synthesis of NiS, has two distinct phases: the first phase
is in the liquid phase at room temperature followed by the second phase which is in the
solid state and is elevated to much higher temperatures, i.e. 150oC.
2.2.1.3.1 Room Temperature, Liquid Synthesis
A solution of Ni(Ac)2 was prepared by dissolving one mmole of Ni(Ac)2 in 50 mL
of methanol, which results in a greenish-blue solution. To this stirring solution, 2mmoles
of 1-hexanethol in 5 mL of ethanol is added drop-wise. After the addition of hexanethiol,
the solution turns a reddish-brown, which is allowed to stir for one hour. Next, 50 mL of
toluene and 50 mL of water is added to the stirring flask. Following the addition of water
and tolene, the water phase is separated from the toluene phase and discarded. To the
remaining toluene phase, 0.1 mmole of sodium sulfide is added and the solution turns a
reddish-black color. Again, the solution is allowed to stir for one hour. Fifty mL of water
is then added to the flask and stirred for 20 more minutes. The water phase is then
separated from the toluene phase and discarded. The toluene phase is then dried in a
rotary evaporator. The dried nanoparticles are rinsed with ethanol and filtered to remove
excess thiol. Toluene was then used to collect the NiS nanoparticles. These
nanoparticles are referred to as C6-NiS (rt, 2X, 0.1X) to denote a room temperature
32
reaction that is a 1:2:0.1 ratio of 1 mmole Ni(Ac)2 to 2 mmoles 1-hexanethiol and 0.1
mmole sodium sulfide.
2.2.1.3.2 Solventless Synthesis of NiS
Larsen and co-workers demonstrated that size- and shape-monodisperse CuS

nanorods could be synthesized using a solventless method.61 The main advantage of
using a solventless method to synthesis semiconductor nanoparticles is the absence of
interparticle collisions which are typical in liquid phase synthesis as both molecular and
nanoparticle diffusion occur very fast in solvent. Hence, in the solventless method,
nanoparticles growth proceeds primarily by monomer addition to the particle surface.61
This procedure has been repeated here for the solventless synthesis of NiS nanoparticles.
Fifty-eight mmoles of Ni(Ac)2 is dissolved in 36 mL of water under vigorous stirring,
which produces a greenish-blue solution. Then, 24.5 mL of chloroform is added to the
stirring solution. To this solution, 80 mmoles of Na+-OOC(CH2)10CH3 is added which
turns the chloroform phase green. The solution is then stirred for 30 minutes. Then the
chloroform phase is separated and collected from the water phase. Eighty-six mmoles of
dodecanethiol is then added to the chloroform phase and stirred for 30 minutes at room
temperature. The chloroform is then removed and the dry nanoparticles are then heated
at various temperatures for different amounts of time. The NiS nanoparticles produced
with this procedure are denoted as C12-NiS (58, 80, 86, 190oC, 45), to denote the starting
amounts of Ni(Ac)2 (58 mmoles) to Na+-OOC(CH2)10CH3 (80 mmoles), and C12H25SH
(86 mmoles), which is heated at 190oC for 45 minutes.
2.2.1.4 HgSe Nanoparticles
33
A solution of Hg(Ac)2 is prepared by dissolving one mmole of Hg(Ac)2 in 50 mL

of ethanol. The Hg(Ac)2 is a light pink solution. To this stirring solution, 2 mmoles of
1-hexanethiol dissolved in 5 mL of ethanol is added drop-wise. The solution then turns
cloudy and is allowed to stir for one hour. Next, 50 mL of toluene and 50 mL of water is
added to the flask. Then the water phase is separated from the toluene phase. To the
toluene phase, a solution of sodium selenide (0.1 mmole in 5 mL of ethanol) is added
drop-wise and results in a greenish brown solution. The reaction flask is allowed to stir
for one hour before the addition of 50 mL of water. The solution is allowed to stir for 20
minutes before the water phase is separated from the toluene phase. The water phase is
discarded while the toluene phase is kept and evaporated using a rotary evaporator
leaving a reddish brown solid or oil in the round bottom flask. The nickel sulfide
nanoparticles were then purified by washing them with methanol in a frit to remove the
excess starting materials. Apolar solvents were used to collect the soluble nanoparticles.
In the case of the oily nanoparticles, it is believed that excess alkanethiol was acting as a
solvent to dissolve the nanoparticles and removal of the alkanethiol was necessary to
produce solid nanoparticles. To remove the excess alkanethiols, hexanes were used to
dissolve the nanoparticles and methanol was dispersed in this solution, mixed vigorously
for several minutes and left to stand for several hours. This allowed the excess
alkanethiol to diffuse to the methanol layer as hexane and methanol are slightly miscible.
The methanol layer (bottom layer) was then removed from the flask and discarded. This
procedure was repeated several times with the best results being produced if the
hexane/methanol solution was allowed to sit overnight before removal of the methanol
layer and if combined with the evaporation of hexanes in a rotorary evaporator. The
34
nanoparticles were then collected by dissolving in toluene. The feed ratio of nickel
acetate was kept fixed at 1 mmol but the feed ratios of alkanethiol and sodium sulfide
were varied and denoted in relation to the nickel acetate. The nanoparticles described
above are referred to as C6-HgSe (rt, 2X, 0.1X) to denote a room temperature reaction
that is a 1:2:0.1 ratio of 1 mmole Hg(Ac)2 to 2 mmoles 1-hexanethiol and 0.1 mmole
sodium selenide.
In the dynamic study, an aliquot was removed from the reaction vessel at various
time intervals after the addition of the Na2S solution, and rinsed with copious amounts of
Nanopure water to remove the starting materials. The water was subsequently removed
and the toluene phase was used for spectroscopic characterizations.
2.2.2 UV-Vis
Uv-Vis spectroscopy was carried out with an ATI UNICAM UV4 spectrometer
with a resolution of 2 nm. In a typical study, 3 mL of chloroform or dichloromethane
was added to a 1-cm quartz cuvette to run a blank. To the cuvette containing the 3mL of
chloroform, a 0.1 mL solution of a 1mg / 1mL solution of nickel sulfide nanoparticles
was added and mixed thoroughly with a pipette. Typically, dichloromethane or
chloroform was used as the solvent for all UV-Vis measurements with the exception of
the dynamic study in which toluene was the solvent.
2.2.3 Fluorescence
Photoluminescence experiments were carried out with a PTI fluorospectrometer.

In these experiments the nanoparticles solutions were prepared in dichloromethane or
chloroform at a concentration of 1 mg/ 1 mL. The solution used for the uv-vis
35
measurements was directly transferred from the UV-Vis cuvette to the fluorescence
cuvette for measurements. For details of solution preparation see section 2.2.3.
2.2.4 Electrochemistry
Electrochemical measurements were carried out with a BAS 100B/W

electrochemical workstation. A carbon electrode (clean or decorated with deposited
nanoparticles and an adsorbed diazonium salt) or a polycrystalline Au disk (sealed in a
glass tubing) was used as the working electrode. A Ag/AgCl wire and Pt coil were used
as the (quasi-) reference and counter electrodes, respectively.
Prior to use, the carbon working electrodes were polished with 0.05m Al2O3
slurries, and subsequently sonicated in water and acetonitrile, successively. The graphite
electrode was then further decorated as discussed in 2.2.1.1 and 2.2.1.2. The blank or
diazonium decorated graphite electrode was placed in a solution of 1mM K4Fe(CN)6,
K3Fe(CN)6, and 0.1 M NH4NO3 and scanned at a rate of 5 200 mV/s. After the Au
MPCs were deposited on the graphite electrode, the working electrode was immersed in a
solution of 0.1 M NH4NO3 for analysis.
The Au working electrode was polished with 0.05 m Al2O3 slurries, and
sonicated in dilute HNO3, H2SO4, and Nanopure water, successively. The electrode was
then subjected to electrochemical etching by applying rapid potential sweeping in 0.10 M
H2SO4 within the potential range of -0.2 to +1.2 V at 10 V/s for 5 minutes. The
electrolyte solution containing MPC nanoparticles was usually prepared at a
concentration of 1 mg/ 1 mL and added to a 0.1 M solution of TBAP.
All solutions were deaerated with high-purity N2 for at least 20 minutes, and
blanketed with a N2 atmosphere during the entire experimental procedure.
36
2.2.5
Thin Film Assemblies
2.2.5.1 Au Langmuir Blodgett Thin Films
Figure 2.6. Schematic of the deposition of Au nanoparticles using the LB technique
Nanoparticle cross-linked networks were fabricated at the air/water interface

using a Langmuir Blodgett trough (NIMA model 611) with a Wilhelmy plate as the
surface-pressure sensor and Nanopure water as the subphase. The details have been
described previously. In a typical experiment, the nanoparticle solutions were prepared
in toluene at a concentration of 1mg/1mL (ca. 14M). An aliquot of 125l was then
spread slowly onto the water surface in a drop wise fashion using a Hamiltonian
microliter syringe. To allow a sufficient evaporation of solvent, twenty minutes was
passed before the addition of the cross linkers. The nanoparticle cross linking was
initiated at high surface pressures after the introduction of bifunctional TBBT ligands.
Typically, 50 L of a 1mg/1ml TBBT solution in CH2Cl2 was spread onto the water
surface with the barrier open (in the 500cm2 position). At least 20 minutes was allowed
for solvent evaporation prior to surface pressure (-A) area isotherm measurements and
between compression cycles. The barrier moving speed was 20 cm2/min
2.2.5.2 Covalent Modification of Carbon Surfaces
The surface of a carbon electrode can be modified by the electrochemical

reduction of diazonium salts, which leads to the covalent attachment of aryl radicals onto
37
the carbon surface. The procedure used to covalently attach an aryl radical onto the
surface of a carbon electrode was given by Allongue and co-workers. The mechanism
for this attachment is given by,
N
N+
+ e-
+ N2
(2.15)
+
(2.16)
To derivatize the surface of a carbon electrode, the graphite electrode is placed in a
solution of 0.1 M TBABF4 and 1mM ethylbenzenediazonium fluoroborate. The details
for the electrochemical set-up are described in 2.2.5. In this case the potential is scanned
at a rate of 83 V/s in the range of -725 -765 mV. This reduction potential window is
negative enough to ensure the reduction of the ethylbenzenediazonium fluoroborate,
which ultimately leads to the covalent attachment of ethylbenzene to the carbon surface,
as demonstrated in 2.15 and 2.16.
38
CHAPTER 3
STRUCTURAL AND ELECTRONIC PROPERTIES OF SILVER
NANOPARTICLES
Reproduced in part with permission from J. Chem. Theory Comput., submitted. Unpublished work
copyright 2007 American Chemical Society.
3.1
Motivation
Silver, a Group IB metal, is a very interesting system to study for numerous

reasons. Electronically, silver has a completely filled d-shell and a single s-valence
electron, which is similar to the electronic structure of the alkali-metals. Hence, silver is
often thought to be analogous to the alkali-metals and considered to be computationally
treated as only an s-metal. This comparison led to many theoretical studies at various
accuracy levels, some studies considered only the s-valence electron while others
included the outer shell d-electrons.
In addition to silvers interesting electronic structure, silver has long used in
photography62,63 and more recently medical imaging,64 hence highlighting the importance
of investigating silvers optical properties in small clusters. Silver also has potential as
an antimicrobial material. Sondi et. al. demonstrated that silver nanoparticles are capable
of damaging E. coli cells.65 In another interesting study, Elechiguerra et. al. were able to
show that silver interacts with HIV-1, which inhibits the binding of the virus to host
cells.66 Commercially, silver has been used as a catalyst for the epoxidation of ethene67,
but the typical lifetime of these catalysts is only 2-3 years before its activity is lost.68 This
degradation of silver particle activity may be better understood by examining which
structures exhibit the best catalytic activity and the conditions under which the structure
changes. Correlating the structural properties to the electromagnetic properties of silver
39
clusters has been a challenge for both experimentalists and theoreticians, but to date
many interesting studies have been published.16,69-79
The relationship between the geometry of a nanoparticle and their properties is
extremely important as the electronic, magnetic, optical, and chemical properties of
noble-metal nanoclusters are highly influenced by size and shape. The ability to predict
and control nanoparticle size is a key component for making the use of nanoparticles in
techonogical applications a reality. Many studies, both experimental and theoretical,
have been completed to shed light on the structure-property relationship. 75,76,80-90 In spite
of these studies, there are discrepancies about the some of the most stable structures for
five and six atom clusters. In addition clusters larger than seven atoms, but smaller than
40 atoms are not routinely studied.
3.1.1
Previous Theoretical Research Related to Silver Clusters
Theoretical studies of small Agn clusters (n = 2 - 12)75,76,80-90 have been carried

out by several groups using different methods and accuracy levels. Those studies
provided a wide variety of results for the most stable structures. For instance, studies
completed by Liao et al81 and Bonacic-Kouteckys et al84 in the early 90s indicate that the
structural evolution from planar to three-dimensional geometries occurs at a cluster size
of five atoms. In particular, they found that the planar trapezoidal structure is most stable
for the five atom cluster while the three-dimensional hexamer is most stable for the six
atom cluster.81,84 However, other studies suggest that the transition actually occurs at a
cluster size of six atoms suggesting the planar hexamer is the most stable
structure.76,80,82,83 Amongst the studies completed most agree upon the structures for Ag3,
Ag4, Ag5, Ag6, and Ag7, but studies of larger clusters, particularly Ag8, Ag9, Ag10, Ag11,
40
and Ag12, indicate that many isomers are possible.80 Hence, there is still a need for a
more thorough investigation of the most stable silver clusters larger than seven atoms.
3.1.2
Previous Experimental Research Related to Silver Clusters
Experimental studies have been completed which confirm the structures predicted
from theoretical calculations for Ag5 70 and Ag7.69 In addition, Peyser et al. were able to
produce Agn clusters (n = 2 - 8 atoms) from AgO films and monitor the fluorescence of
these clusters.8,91 The electronic structure of Agn clusters (n = 1-21) was explored
Handschuh et al. using photoelectron spectroscopy.92 These types of successes in the
laboratory expedite the need for systematic theoretical studies of small clusters for three
reasons. First, theoretical studies can assist the interpretation of the experimental results.
Secondly, these experimental results can be used as a benchmark for evaluating different
computational methods. Third, the structure cannot be determined by experiment for
these small clusters without assistance from theoretical calculations, so many sizes and
shapes must be studied for comparison.
3.2 Results and Discussion
The most stable linear, planar, and three-dimensional structures as well as their
corresponding binding energies, magnetic moments, HOMO-LUMO energy gap, and
coordination numbers are given in Tables 3.1 3.3. Within these tables the structures are
arranged according to their dimensionality and stability. For example Table 3.1, Table
3.2, and Table 3.3 contain the structure and corresponding properties for the linear,
planar, and three-dimensional structures, respectively. Within each table the notation iMN
is used to categorize the various clusters, where M is the dimensionality, L for linear, P
for planar, and T for three-dimensional. The subscript N is the number of atoms in the
41
cluster (also referred to as cluster size), and the superscript, i, is the ith isomer at a given
cluster size. Further, i is omitted in the notation if only one structure is studied at that
given size. The isomers are arranged such that the most stable structure is the first isomer
in the group and subsequent isomers are arranged in decreasing stability, i.e. 1P5 is the
most stable planar pentamer.
3.2.1 Linear Ag Clusters
As shown in Table 3.1, the smallest linear Ag cluster is a dimer and has a bond
length of 2.57 , which is in good agreement with the experimental Ag dimer bond
length, 2.533350.04 93 or 2.5303 94. The GGA DFT calculation only slightly
overestimates the dimer bond length, by approximately 0.04 , which is not surprising as
the GGA has a tendency to overestimate bond lengths.22 Amongst other computational
studies various bond lengths are found for the Ag dimer: 2.49 85, 2.52 95, 2.53 96,
2.57 72, and 2.612 84. Although, the dimer bond length agrees well with experiment,
the calculated dissociation energy, 1.80 eV, is much higher than the experimental
dissociation energy of the Ag dimer, 1.66 eV 97,98 or 1.67 eV99, indicating an
overestimation of bonding in the dimer.
As the linear chains grow from three atoms, a Peierls bond distortion causes an
alternation of short and long bond lengths within a chain. For example, the bond length
at the end of L4 is 2.60 , while the bond length between the second and third atom of the
L4 chain increases to 2.71 , but again decreases to 2.60 between the third and fourth
atoms. This lowering of symmetry of the one-dimensional chain allows its energy to be
lowered. To confirm that the linear chains undergo Peierls bond distortion, the binding
strength of the chains is examined by considering four different interactions: Ag-Ag
42
dimer, between a Ag atom and a Ag dimer, between two Ag dimers, and between a Ag
atom and two Ag dimers. The Ag-Ag dimer interaction is demonstrated by L2 in Table
3.1. The binding energy for the Ag-Ag dimer interaction is 1.80 eV. The interaction
between a Ag dimer and a Ag atom is shown by L3 in Table 3.1. To determine the
binding energy of the interaction between the Ag dimer and Ag atom, the binding energy
of L2 was subtracted from L3 with a proper conversion of units and is 0.84 eV. The
interaction between two Ag dimers, as shown by L4 in Table 3.1 has a binding energy of
1.92 eV, which was found by subtracting the energy of two L2 from that of L4. The
interaction between a Ag atom and two dimers, as illustrated by the center Ag atom of L5
in Table 3.1 has a binding energy of 1.5 eV, which was determined by subtracting the
binding energy of two L2 from that of L5. These four different interactions were then
used to calculate the binding energies per atom for L6 L9, which are 1.06 eV/atom, 1.03
ev/atom, 1.08 eV/atom, and 1.07 eV/atom, respectively. These values are all close to
their respective DFT values, which is an indication that these types of interactions can be
used to describe the bonding nature in linear Ag clusters. Furthermore, these results
confirm that Ag linear chains indeed undergo a Peierls distortion. In addition to the
Peierls bond distortion seen in Ag chains, gold, another coinage metal, also exhibits
Peierls bond distortion.100
43
Table 3.1. The structure, coordination number (Coord #), binding energy (EB), HOMO-
LUMO energy gap (EG), and the magnetic moment () of linear clusters. The inserted
bond lengths are in .
Notation
Structure
2.57
L2
L3
2.63 2.63
L4
2.60 2.71 2.60
L5
2.62 2.67 2.67 2.62
L6
2.60 2.69 2.62 2.69 2.60
L7
2.61 2.68 2.65 2.65 2.68 2.61
L8
2.61 2.70 2.64 2.69 2.64 2.70 2.61
L9
Coord
#
EB
(eV/atom)
EG
(eV)
(B/atom)
1.00
0.90
2.06
0.00
0.73
0.88
2.09
0.33
1.50
1.02
1.10
0.00
1.60
1.02
1.27
0.20
1.67
1.07
0.78
0.00
1.71
1.07
0.83
0.14
1.75
1.09
0.56
0.00
1.78
1.09
0.67
0.11
2.61 2.69 2.65 2.67 2.67 2.65 2.69 2.61
3.2.2 Planar Ag Clusters
Structural information, binding energies, HOMO-LUMO energy gaps, and

magnetic moments of 45 planar Ag clusters as large as 16 atoms are summarized in Table
3.2. The most stable planar structures all contain triangular units which are significantly
more stable than structures that are dominated by square units, indicating that the
triangular unit is an ideal building block for larger planar Ag clusters. For instance, the
most stable tetramer structure of the planar clusters is the rhombus which has a higher
binding energy by 0.18 eV/atom than the square structure. Interestingly, the linear trimer
is just as stable as the planar trimer; however, after three atoms the planar structures are
significantly more stable than the linear chains. Our most stable pentamer, the planar
trapezoid, was also found to be the most stable pentamer during resonance Raman studies
44
of Ag5 clusters isolated in rare gas matrices.70 Also, other theoretical works produce the
planar trapezoid75,82,101 as the most stable pentamer.
Our studies of the silver trimer 1P3, indicate that the most stable planar structure is
an obtuse triangle with the largest bond angle of 69.63o and two short bond lengths of
2.64. This result is in good agreement with other experimental studies and theoretical
studies which indicate that the silver trimer is a distorted isosceles triangle, perhaps even
an obtuse triangle.80,102-105 Although the most stable planar trimer is an obtuse triangle
this structure is only slightly more stable than the corresponding equilateral triangle and
linear trimer, which is an indication of how easily silver atoms can change configuration.
The most stable structures for the tetramer, pentamer, and hexamer, were found to
be the rhombus, the trapezoid, and a planar D3h triangle, respectively, which is in
agreement with previous studies.80 Successive building on the D3h triangle produces
many of the most stable larger clusters.
45
Table 3.2. The structure, symmetry, bond length (BL ), binding energy (EB), HOMO-
LUMO energy gap (EG), magnetic moment (), and the coordination number (Coord. #)
of different planar clusters.
Notation
C1h
2.63-2.64
0.89
0.29
0.33
1.33
C2V
2.63
0.88
0.00
0.33
2.00
D2h
2.62-2.74
1.17
0.85
0.00
2.50
D2h
2.68
0.99
2.01
0.50
2.00
C2v
2.69-2.76
1.28
1.35
0.20
2.80
C2v
2.68-2.71
1.24
1.32
0.20
2.40
D2h
2.68-2.71
1.20
0.81
0.20
2.40
C2v
2.69-2.80
1.46
2.18
0.00
3.00
C2h
2.73-2.81
1.28
0.50
0.00
3.00
D2h
2.63-2.79
1.26
0.86
0.00
2.33
D2h
2.66-2.70
1.24
1.57
0.33
2.67
C1h
2.68-2.77
1.42
1.12
0.14
3.14
D2h
2.70-2.78
1.42
0.08
0.14
3.43
C2v
2.62-2.74
1.27
0.88
0.14
2.57
C1h
2.69-2.83
1.50
0.81
0.00
3.50
D2h
2.68-2.78
1.49
1.16
0.00
3.00
C2v
2.61-2.83
1.40
0.57
0.00
3.00
D2h
2.66-2.78
1.34
0.51
0.00
2.75
D2h
2.64-2.69
1.32
0.51
0.00
2.50
D2h
2.68-2.87
1.49
0.12
0.11
3.56
P3
P3
P4
P4
P5
P5
P5
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
Notation
P5
P6
P6
P6
P6
P7
P7
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
D4h
2.61
1.00
1.28
0.20
4.00
1.6
Notation
P7
P8
P8
P8
P8
P8
P9
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
46
Table 3.2. (continued)

Notation
C2v
2.67-2.83
1.48
0.98
0.11
3.56
D4h
2.65-2.73
1.39
0.15
0.11
2.67
C2v
2.65-2.73
1.31
0.23
0.11
2.67
D2h
2.74-2.83
1.59
1.31
0.00
3.80
C1h
2.67-2.80
1.57
1.33
0.00
3.60
C2v
2.74-2.83
1.48
1.78
0.20
3.60
D2h
2.68-2.70
1.36
0.47
0.00
2.80
D2h
2.62-2.75
1.32
0.32
0.00
2.60
C1h
2.71-2.83
1.57
0.16
0.09
3.82
D2h
2.69-2.89
1.54
0.60
0.09
0
3.64
C2v
2.68-2.76
1.53
1.21
0.09
3.27
C2v
2.73-2.77
1.64
1.07
0.00
4.00
C2h
2.69-2.84
1.60
1.01
0.00
3.83
C2v
2.71-2.82
1.55
0.59
0.17
3.83
D2h
2.65-2.73
1.46
0.26
0.00
2.83
C1h
2.73-2.81
1.62
1.45
0.08
4.00
C1h
2.67-2.85
1.57
0.18
0.08
3.85
D2h
2.68-2.82
1.63
0.15
0.00
4.14
C2v
2.69-2.81
1.60
0.28
0.00
4.00
C1h
2.69-2.83
1.65
0.62
0.07
4.13
C1h
2.67-2.85
1.64
0.35
0.07
4.13
P9
P9
P9
P10
P10
P10
P10
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
Notation
P10
P11
P11
P11
P12
P12
P12
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
Notation
P12
P13
P13
P14
P14
P15
P15
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
47

Notation
C1h
2.71-2.82
1.58
0.4171
0.07
4.00
C1h
2.70-2.85
1.70
0.36
0.00
4.13
C1h
2.69-2.85
1.67
0.34
0.00
4.00
P15
P16
P16
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
3.2.3 Three-dimensional Ag Clusters
The structural information, binding energies, HOMO-LUMO energy gaps, and

magnetic moments of 90 three-dimensional Ag clusters up to 16 atoms are summarized in
Table 3.3. As the three-dimensional cluster size becomes larger than eight atoms a wide
variety of structures are studied for each cluster size, yet many structures have similar
binding energies. For instance, the most stable nonamer has a binding energy of 1.56
eV/atom, while ten other nonamers are within 0.04 eV/atom of the highest energy
nonamer. Hence, it is very difficult to pinpoint the most stable structure for clusters
larger than eight atoms. This trend also indicates that the surface atoms for these clusters
are fluidlike and can easily reconfigure by undergoing successive isomer
interconversions, indicating that several geometries will be stable and possible to produce
in experiment. Although it is difficult to pin point one particular structure to be the global
minimum for larger clusters it is interesting that our most stable clusters, 1T9, 1T10, 1T11,
1
T13, 1T14, 1T15, and 1T16, are different than the most stable structures found in other
studies.80
48
Table 3.3. The structure, symmetry, bond length (BL), binding energy (EB), HOMO-
LUMO energy gap (EG), magnetic moment (), and the coordination number (Coord. #)
of different three-dimensional Ag clusters.
T4
Symmetry
BL ()
C2v
2.77
C2v
2.63-2.85
Cs
2.61-2.86
C4v
2.71-2.84
C5v
2.70-4.57
D2h
2.72-4.72
EB(eV/atom)
EG(eV)
0.91
2.19
0.50
3.00
1.17
0.09
0.20
3.60
1.17
0.02
0.20
5.33
1.13
0.65
0.20
5.33
1.42
1.80
0.00
3.33
1.28
0.50
0.00
3.00
C2h
2.73-2.76
1.25
1.30
0.33
3.33
Oh
2.80
1.24
1.80
0.33
4.00
C2v
2.72-3.88
1.21
2.03
0.33
3.00
C3v
2.79-2.92
1.49
1.15
0.14
4.29
C1
2.75-2.86
1.46
1.39
0.14
4.29
C3v
2.75-2.88
1.42
1.37
0.14
4.00
Symmetry
BL ()
EB(eV/atom)
C3v
2.70-2.78
1.40
C1
2.77-2.87
1.59
C2v
2.72-2.88
1.57
C2v
2.70-2.83
1.56
C2v
2.76-2.90
1.56
C1
2.68-2.90
1.56
EG(eV)
0.99
0.14
3.43
2.27
0.00
4.50
1.67
0.00
4.50
1.31
0.00
4.00
1.97
0.00
4.00
1.26
0.00
4.50
Notation
T5
T5
T5
T6
T6
Structure
(B/atom)
Coord. #
Notation
T6
T6
T6
T7
T7
T7
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
Notation
T7
T8
T8
T8
T8
T8
Structure
(B/atom)
Coord. #
49

Notation
C4v
2.73-2.82
1.54
1.83
0.00
4.00
D3d
2.72
1.46
0.74
0.00
3.00
C2v
2.70-2.87
1.37
1.53
0.25
3.75
C2v
2.75-2.90
1.59
1.87
0.11
3.78
C1
2.72-2.91
1.56
0.99
0.11
4.67
C1
2.72-2.90
1.56
1.10
0.11
4.67
C1
2.76-2.89
1.55
0.51
0.11
4.67
C2v
2.78-2.95
1.55
0.51
0.11
4.89
C1
2.78-2.87
1.55
0.46
0.11
4.89
C1
2.74-2.91
1.55
0.40
0.11
4.67
C1
2.75-2.92
1.54
0.36
0.11
4.67
C1
2.74-2.90
1.54
1.05
0.11
4.67
10
11
12
13
14
15
C1
2.75-2.91
1.54
0.30
0.11
4.67
C1
2.74-2.88
1.54
0.41
0.11
4.44
C1
2.74-2.90
1.54
0.31
0.11
4.67
C1
2.70-2.96
1.53
1.12
0.11
4.67
C1
2.73-2.85
1.53
0.23
0.11
4.22
C2v
2.79-2.90
1.49
0.18
0.11
4.67
T8
T8
T8
T9
T9
T9
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
Notation
T9
T9
T9
T9
T9
T9
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
Notation
T9
T9
T9
T9
T9
T9
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
50

Notation
16
C4v
2.70-2.87
1.44
0.21
0.11
3.56
C2v
2.84-2.87
1.62
1.31
0.00
4.60
C1
2.78-2.96
1.62
0.98
0.00
5.20
C1
1.98-2.96
1.61
1.09
0.00
4.60
C1
2.76-2.94
1.61
1.08
0.00
4.80
C1
2.72-2.94
1.61
0.78
0.00
4.60
10
11
C1
2.74-2.96
1.61
0.93
0.00
4.60
C1
2.72-2.88
1.60
0.77
0.00
4.80
C4v
2.61-2.87
1.60
0.77
0.00
4.80
C1
2.69-2.91
1.60
0.70
0.00
4.80
C1
2.69-2.96
1.59
1.02
0.00
4.80
C2h
2.70-2.81
1.57
0.65
0.00
4.00
12
13
14
15
16
17
C1
2.77-2.88
1.56
0.54
0.20
4.80
C1
2.72-2.99
1.55
0.49
0.00
4.60
C1
2.73-2.97
1.54
0.33
0.20
5.20
C1h
2.71-2.99
1.52
0.23
0.00
4.80
C1
2.72-2.99
1.52
0.21
0.20
4.80
C2v
2.70-2.77
1.43
0.76
0.00
3.40
T9
T10
T10
T10
T10
T10
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
Notation
T10
T10
T10
T10
T10
T10
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
Notation
T10
T10
T10
T10
T10
T10
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
51

Notation
18
C2v
2.66-2.72
1.34
0.09
0.20
3.00
C1h
2.77-2.84
1.64
0.62
0.09
4.91
C1
2.77-2.89
1.63
0.85
0.09
4.91
C1
2.70-2.98
1.62
0.44
0.09
5.09
C1
2.71-2.91
1.60
0.39
0.09
4.91
C1
2.66-2.98
1.57
0.28
0.09
4.18
C1
2.68-2.99
1.55
0.33
0.09
4.72
C2v
2.73-2.91
1.46
0.07
0.27
4.55
C1
2.76-2.99
1.67
0.84
0.00
5.00
C1
2.72-2.96
1.67
0.82
0.00
4.67
C1
2.71-2.96
1.66
0.64
0.00
5.17
C1
2.72-2.97
1.66
0.65
0.00
4.83
10
Cs
2.73-2.89
1.65
0.79
0.00
4.83
C1
2.72-2.96
1.63
0.31
0.00
5.67
C1
2.76-2.98
1.63
0.29
0.00
5.67
Cs
2.74-2.96
1.63
0.78
0.00
5.00
C1
2.66-2.99
1.62
0.71
0.00
4.83
C1
2.73-2.96
1.62
0.45
0.00
4.67
T10
T11
T11
T11
T11
T11
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
Notation
T11
T11
T12
T12
T12
T12
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
Notation
T12
T12
T12
T12
T12
T12
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
52

Notation
11
12
13
14
15
16
C1
2.77-2.92
1.61
0.42
0.17
5.50
C1
2.70-2.99
1.60
0.41
0.00
5.17
D4h
2.79-2.89
1.60
0.44
0.00
4.33
C1
2.68-2.98
1.57
0.12
0.00
4.83
C2h
2.75-2.88
1.54
0.09
0.33
5.00
D2h
2.68-2.77
1.50
0.82
0.17
1.67
T12
T12
T12
T12
T12
T12
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
Notation
T13
T13
T13
T13
T14
T14
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
# of Bonds
Coord. #
Notation
C4v
2.74-2.83
1.65
0.93
0.08
32
4.92
Cs
2.85-2.99
1.63
0.58
0.08
28
4.31
D4h
2.82-2.90
1.60
0.49
0.08
36
5.54
C4v
2.71-2.80
1.54
0.95
0.08
24
3.69
C2v
2.65-2.96
1.69
0.88
0.00
35
5.00
C1
2.70-2.99
1.69
0.32
0.00
34
4.88
Cs
2.73-2.98
1.65
0.61
0.00
5.00
C2v
2.65-2.96
1.65
0.20
0.00
5.14
C1
2.74-2.96
1.70
0.38
0.07
5.33
C1
2.71-2.92
1.73
1.13
0.13
5.25
C1
2.75-2.91
1.72
1.12
0.13
5.25
C1
2.72-2.86
1.69
0.83
0.13
5.00
T14
T14
T15
T16
T16
T16
Structure
Symmetry
BL ()
EB(eV/atom)
EG(eV)
(B/atom)
Coord. #
53
3.2.4 General Discussion
The binding energy of linear, planar, and three-dimensional Ag clusters, shown in

Figure 3.1, increases with cluster size in a staircase manner: moving from an even cluster
to an odd cluster forms the rise of the staircase while moving from an odd cluster to an
even cluster forms the run of the staircase. Figure 3.1 also indicates that Ag clusters
smaller than seven atoms prefer a planar geometry while clusters larger than seven atoms
prefer a three-dimensional geometry. This transition from Ag clusters preferring planar
geometries to three-dimensional geometries supports previous findings that the D3h
triangle, 1P6, is more stable then the pentagonal pyramid, 1T6.72,75,76,80,87,101,106 The
discrepancy lies in the fact that some studies find the three-dimensional pentagonal
pyramid more stable than the planar hexamer, 1P6.
1.8
EB (eV/atom)
1.6
1.4
1.2
1.0
0.8
2
10
12
14
16
Cluster Size n
Figure 3.1. The binding energy, EB, as a function of cluster size for the linear (),
planar (), and three-dimensional () Ag clusters. In each dimensionality we plot the

most stable isomer among all the available ones
54
The HOMO-LUMO energy gap is an important electronic property and is plotted

for the most stable linear, planar, and three-dimenisonal Agn (n = 2 16) clusters as
shown in Figures 3.2 3.4. The trend for the HOMO-LUMO energy gap is quite
pronounced for the linear chains, which demonstrate an even odd oscillation that
decreases as the cluster size increases. The energy gap for the silver dimer is 2.06 eV,
which is much larger than bulk silver which has a zero band gap energy. However, as the
chain sizes increases to nine atoms, the HOMO-LUMO energy gap has already decreased
significantly to 0.67 eV. The odd linear clusters tend to have a larger HOMO-LUMO
energy gap than their even-numbered clusters. The HOMO-LUMO energy gap for planar
clusters does not demonstrate the same even-odd oscillation found in the linear chains;
however, an approximate even-odd oscillation does occur for clusters larger than six
atoms. The largest HOMO-LUMO energy gap for planar clusters occurs for the hexamer
with a value of 2.18 eV. Calculated HOMO-LUMO energy gaps for the threedimensional clusters as a whole tend to be larger than both the planar and linear chains,
but do not show an even-odd oscillation. In addition to plotting the HOMO-LUMO
energy gaps of the most stable isomers as a function of cluster size for each
dimensionality, the HOMO-LUMO energy gap was also monitored for the most stable
isomer of a given size regardless of dimensionality, as shown in Figure 3.5.
55
2.4
EG(eV)
2.0
1.6
1.2
0.8
0.4
2
10
Cluster Size n
Figure 3.2. The HOMO-LUMO energy gap, EG, as a function of cluster size for the most
stable Ag linear chains.
2.4
2.0
EG(eV)
1.6
1.2
0.8
0.4
0.0
2
10
12
14
16
18
Cluster Size n
stable Ag planar clusters.
56
2.4
2.0
EG(eV)
1.6
1.2
0.8
0.4
0.0
10
12
14
16
18
Cluster Size n
stable three-dimensional Ag clusters.
HOMO-LUMO Gap (eV)
2.5
2.0
1.5
1.0
0.5
0.0
2
10
12
14
16
Cluster Size n
stable Ag clusters among all dimensionalities.
57
In systems of smaller size and reduced dimensionality the magnetic moment is

expected to be larger than the corresponding bulk.18 Figures 3.6, 3.7, and 3.8 depict the
magnetic moments as a function of size for Ag linear, planar, and three-dimensional
clusters, respectively. With the exception of 1T4 and 1T16 the most stable even numbered
clusters have a magnetic moment of zero, however, the magnetic moment of the most
stable odd-numbered clusters decreases with cluster size for all dimensionalities. The
magnetic moments of the most stable even numbered clusters are zero with the exception
of 1T4 and 1T16. In contrast the odd numbered clusters have a nonzero magnetic moment
which decreases with cluster size. This is not surprising due as the odd-numbered Ag
clusters have an unpaired electron in contrast to the paired electrons found in evennumbered clusters.
0.35
0.30
(B/atom)
0.25
0.20
0.15
0.10
0.05
0.00
2
Cluster Size n
linear chains.
58
0.35
0.30
(B/atom)
0.25
0.20
0.15
0.10
0.05
0.00
2
10
12
14
16
Cluster Size n
planar clusters.
0.5
(B/atom)
0.4
0.3
0.2
0.1
0.0
4
10
12
14
16
Cluster Size n
three-dimensional clusters.
59
Many studies have been conducted for Agn clusters with n 12, using a variety of
computational methods and various basis sets, yet as the clusters become larger than 7
atoms there is some dispute about the most stable structures. It is our intention to
compare our results for each cluster size with the results of studies that used different
methods106 and/or basis sets80,85,87, as well as the experimental bulk cohesive energy,
which is 2.95eV.80 Table 3.4 shows the most stable structure at each cluster size and the
corresponding binding energies of these clusters from different references. Starting with
the three-atom silver cluster, a simple triangle; the binding energies for these different
DFT calculations are in pretty good agreement with each other, however, the DFT
calculation with an LDA basis set yields a much higher binding energy. A similar trend
is followed for the four atom rhombus; the LDA basis set yields the much higher binding
energy. From Bonacic-Koutecky87, we can also compare the different basis sets used in
the various DFT calculations with CCSD calculations for the five atom trapezoid. Here
the BLYP basis set yields the same result as the CCSD calculation; the LSD and PW
form of the GGA are slightly lower in energy than the CCSD calculation, but the BPW
and LDA basis sets are much lower and higher in energy, respectively, than the CCSD
calculation. This same trend holds true for the hexamer. For the heptamer the CCSD
binding energy is closest to the PBW basis set and is much lower than all of the other
basis sets. Although the structures are not exactly the same, they are very similar for the
octamer. The octamer the BLYP basis set yields a higher binding energy than the CCSD
calculation and the LSD basis set is nearly the same as the CCSD calculation. Again, the
PW and PBW basis sets yield a slightly lower binding energy. As the cluster size
60
increases the PW basis set is consistently lower in energy than other basis sets, but it is
only 55% of the bulk cohesive energy for the decamer, whereas, the binding energy from
the LDA basis set is much at 79% and the LSD basis set is 65% of the bulk cohesive
energy. Naturally, as the cluster size increases the binding energy should approach that
of the bulk cohesive energy, but the binding energy should not be close to the bulk
cohesive energy at cluster size of ten atoms.
61
Table 3.4. Binding energies, EB, of the most stable structures from different methods and
functionals
EB1
(eV/atom)
EB2
(eV/atom)
EB3
(eV/atom)
EB4
(eV/atom)
EB5
(eV/at
om)
0.88
0.88
0.82
1.33
NA
1.17
1.20
1.08
1.69
NA
1.35
1.40
1.19
1.83
1.49A
1.49B
1.46
1.55
1.36
2.04
1.72A
1.69B
1.48
1.60
1.38
2.15
1.65A
1.34B
1.58
1.58
1.57
1.59
1.80
1.48
2.17
2.00A
1.81B
1.78
1.45
2.09
NA
10
1.62
1.62
1.90
1.51
2.34
NA
11
1.64
1.92
1.52
NA
NA
12
1.67
2.00
1.57
NA
NA
Cluster
Size(N)
Most Stable Structures
Our work
Ref. 31 DFT: LSD(VWN) 3Ref 55 DFT: GGA(BPW) 4Ref. 36 DFT: LDA
Ref 38 A DFT (BLYP) BCCSD. Note: Bold and Italic entries are different structures
then our most stable structures
62
3.3 Summary
From this work we have shown that linear clusters undergo Peierls bond
distortion, that planar clusters prefer a high coordination number and triangular
configurations, and that larger three-dimensional silver clusters are fluidlike and may
adapt many different configurations. Also, our results are in agreement with other studies
indicating that the planar hexamer is more stable than other three-dimensional structures.
In addition the magnetic moments were shown to be higher for small clusters and
oscillate between paramagnetism and diamagnetism for odd and even clusters,
respectively.
3.4 Future Research Directions
Silver clusters have studied extensively for sizes smaller than eight atoms,
therefore, continuing to study the structural characteristics of clusters larger than eight
atoms should be continued to be investigated for neutral and ionic silver clusters. In
addition to the binding energies, the HOMO LUMO energy gap, and the magnetic
moment, other properties could be studied: ionization potentials, fragmentation energies,
harmonic frequencies, and electron affinities. Also, the study of three-dimensional
nanotubes and nanowires would be interesting.
63
CHAPTER 4
COALESCENCE OF SILVER NANOPARTICLES USING MOLECULAR
DYNAMIC SIMULATION
Reproduced in part with permission from J. Chem. Theory Comput. 2007, 3, 328-335. Copyright 2007
American Chemical Society. Reproduced in part with permission from J. Phys. Chem C, in press.
Unpublished work copyright 2007 American Chemical Society.
4.1 Motivation/Background
During the synthesis of metal clusters, regardless of method, the growth process is
critical in the formation of stable, mono-disperse clusters. The manner in which the
clusters grow can be dominated by a variety of mechanisms. Two interesting processes
are Ostwald ripening and coalescence. Ostwald ripening involves the diffusion of a
single atom from one cluster to another cluster. This type of growth is seen in the
coarsening of thin films and size evolution of nanoparticles in the liquid phase. The key
aspect of Ostwald ripening is that overtime the average cluster size increases due to the
growth of larger clusters at the expense of smaller ones.
Coalescence involves the collision of one cluster with another cluster. The
aftermath of such a collision can lead to a range of products or stages of cluster growth.
During the nucleation stage, the formation of a larger cluster from the collision of two
clusters is difficult and is dependent on the removal of excess heat from the system. In
contrast, the cluster growth stage is characterized by the formation of a larger cluster and
is spontaneous. During the cluster growth stage, the formation of a larger cluster is not
dependent on the removal of excess heat, although the removal of heat affects the final
structure. The final stage is the termination of growth in which larger clusters are no
longer formed. The termination of cluster growth usually occurs because the colliding
64
clusters are already large themselves and the thermodynamic constraint of the system
makes the formation of an even larger cluster unfavorable. Therefore, the cluster growth
becomes non-spontaneous.
We chose to investigate the formation of silver nanoparticles of different sizes
using molecular dynamic simulations (MD) with a Sutton-Chen potential in order to
distinguish the size range at which the nucleation and cluster growth is dominant as well
as the dependence of product formation on the impact energy and incident angle.
4.1.1
Previous Theoretical Research on Coalescence
Computationally, a wide range of investigations into the coalescence of different

metal clusters have been completed.28,107-119 Among the these studies, several aspects of
nanoparticle coalescence have been studied: the energetics during
coalescence110,112,113,118,120,121the kinetics of the coalescence process107,109,111,113,114,119, the
effects of internal pressure109, importance of temperature107,111-113,115,118,119, and size
dependence109-111,116,119,122 For instance, Lehtinen and co-workers studied the thermal
behavior of coalescing nanoparticles and include the effect of energy release during
coalescence. They found that the coalescence is driven by the minimization of surface
energy which is reflected in the temperature increase in the resulting particle and greatly
affects the overall coalescence process.113 Hendy and co-workers also found that the
temperature of the daughter cluster is higher than the temperature of the parent clusters,
which aides in atomic diffusion during coalescence.113 After studying the coalescence of
gold nanoparticles, Liu and co-workers proposed a new simulation strategy that better
reproduces the results from experimental coalescence data.115 Tian and co-workers also
studied the effect of different temperatures on the coalescence of metal clusters, but they
65
also investigated clusters supported on a substrate.119 Interestingly, they found that the
coalescence process was not only dependent on the cluster size but also the average
binding energy of the clusters.119 In addition to the thermal properties of nanoparticles,
Ehrman investigated the effect of internal pressure on estimating the rates of
coalescence.109 From these studies Ehrman determined that as the internal pressure of the
cluster increases the predicted particle also increases.109 Despite these findings there is a
lack of understanding of the distinguished stages of cluster growth.
4.2 Potential Energy Surface Construction
One requirement and the most time consuming task of MD simulation is the
computation of the force acting on every particle in the system. Although the calculation
of the force or potential, on every particle is time consuming it is one of the most
significant factors in determining the accuracy of the results obtained from the MD
simulation, hence it is important to use appropriate models for the system studied. In my
research, the potential energy surface of silver clusters was calculated using the Sutton
Chen potential, which has been designed specifically for transition metals.55 The Sutton
Chen model has parameters , c, m, n, and a, which were obtained from fitting the
properties of the bulk structure.55 For instance, the parameter a is the bulk lattice
constant and is fitted to the cohesive energy, and c is fitted to an equilibrium condition
of the lattice sum of a perfect f.c.c. crystal. The parameters fitted from the bulk
properties of silver by Sutton and Chen are shown in Table 4.1.
66
Table 4.1. Sutton-Chen potential parameters obtained from the bulk and from fitting the
parameters to DFT data.

Parameters
m
n
(eV)
c
a ()
Bulk Parameters
6
12
2.5415x10-3
144.41
4.09
Cluster Parameters
6
12
1.8828x10-3
144.36
4.04
In this research, the silver clusters studied are considerably smaller and of different
geometry than the bulk crystal that the Sutton-Chen parameters were derived from.
Hence, the potential energy surface derived from the Sutton-Chen potential with bulk
parameters may not be suitable for MD simulations of Ag clusters. To investigate the
accuracy of the Sutton-Chen potential, the binding energy of the Ag dimer was calculated
using DFT and the Sutton-Chen potential and then compared to the experimental value.
As indicated in Chapter 3, the DFT calculation for the bond distance of the Ag dimer
agrees well with the experimental value and the calculation of the binding energy only
slightly overestimates the dissociation energy of the dimer. However, the binding energy
obtained from the Sutton-Chen potential for the dimer with a bond length of 2.57 is
2.29 eV, which is much larger than the experimental value of 1.65 eV.
In addition to the Ag dimer, we calculated the binding energy of the linear trimer, L3
from Chapter 3, the planar trimers, 1P3 and 2P3 from Chapter 3, and dimers of various
bond lengths using the Suton-Chen potential to compare with their corresponding DFT
values. The binding energies of the linear, L2 and L3, and planar structures, 1P3 and 2P3,
67
calculated using the Sutton-Chen potential and DFT are shown in Table 4.2. For each of
these structures the Sutton-Chen potential significantly overestimates the binding energy;
the largest overestimation is of the equilateral triangle by 1.21 eV. In addition the linear
trimer, L3, and the equilateral triangle, 2P3, should be degenerate in energy, but the
Sutton-Chen predicts that the planar structure, 2P3, should be more stable than the linear
trimer.
Figure 4.1 illustrates how the potential energy calculated using DFT and the SuttonChen potential varies as a function of dimer bond length, 1.0 - 4.0 . As shown in Figure
4.1, the potential energy calculated using the Sutton-Chen potential does not agree with
the DFT results. These results combined with the above discussion suggest that a
modification of the Sutton-Chen potential is needed. Therefore, as a first attempt, we
optimized the parameters , a, and c of the Sutton-Chen potential by fitting them to the
DFT results, however, the parameters m and n are kept the same as those given by Sutton
and Chen. To complete this task we used the Levenberg-Marquardt algorithm54, a
nonlinear fitting method as discussed in Chapter 2. The linear and planar structures in
Table 4.2 were used to fit the new parameters.
The term cluster parameters is used to denote the Sutton-Chen parameters fitted to
the DFT results. These new parameters, shown in Table 4.1 are used to construct a new
PES for Ag. Using the cluster parameters, the binding energies of 1P3, 2P3, L2, and L3 are
calculated, and again compared to the DFT results. Table 4.2 contains these new binding
energies, which are dramatically improved. The binding energy for all structures is
significantly lowered; the maximum deviation in binding energy is 0.4 eV, which is much
lower than the maximum deviation from the Sutton-Chen bulk parameters, 1.21 eV. In
68
addition, the binding energies for 2P3 and L3 are now practically degenerate with an
overestimation of only 0.1 eV.
Table 4.2. Binding energies, EB (eV), for the most stable clusters containing three atoms
calculated using DFT and the SC potential with bulk parameters and cluster parameters.
Structure
L2
1
P3
2
P3
L3
DFT (eV)* SC: bulk (eV) SC: cluster (eV)

1.80
2.29
1.68
2.67
4.15
3.04
2.64
3.85
2.74
2.64
3.73
2.73
*DFT values from Table 3.1 3.2.
Figure 4.1 depicts the potential energy calculated using DFT and the Sutton-Chen
potential using the bulk and the cluster parameters as a function of dimer bond distance.
Obviously, the binding energies calculated using the cluster parameters are in much
better agreement with the DFT data. Hence, using the cluster parameters can improve the
potential energy surface for use in calculations of small silver clusters. The potential
energy surface for Ag is shown in Figure 4.2 using the Sutton-Chen bulk parameters and
the cluster parameters. Although, an improvement has been made, the potential energies
calculated with the cluster parameters are still not an exact match to the DFT results.
69
V (eV)
-1
-2
r (A)
Figure 4.1. The potential energy as a function of interatomic distance from DFT
calculations () and calculations using the Sutton-Chen potetential with bulk parameters
(solid line) and cluster parameters (dashed line).
70
8
-2
0
2
4
6
8
10
rBC
rBC
3
2.0
2.5
3.0
3.5
4.0
rAB
Figure 4.2. The silver cluster optimized (bottom) and original bulk (top) Sutton-Chen
PES for the collinear AB + C reaction. The legend shows the potential energy in eV.
The interatomic distances rAB and rBC are given in angstroms, .
4.2.1 Potential Energy Surface Impact on the 3-Atom System
As an additional investigation of the impact of the PES, the coalescence of a 3atom system was studied using MD simulation. This 3-atom system consists of a single
atom, C, colliding with a dimer, AB, as shown in Chapter 2. The anticipated products
from this coalescence, shown in Figure 4.3, can be divided into two categories: non-
71
reactive and reactive scattering. The non-reactive scattering products can be sub-divided
into elastic scattering and inelastic scattering products.
AB() + C
(1) AB() + C: Elastic Scattering

(2) AB() + C: Inelastic Scattering Non-reactive Scattering
(3) A + B-C()
(4) A-B-C
Reactive Scattering
(5) A + B + C
Figure 4.3. Classifications of the possible products for the coalescence of a single atom,
C, and a dimer, AB, with vibrational frequency, .
In order to set-up the initial coordinates the equilibrium bond distance of AB must
first be determined. This equilibrium bond distance is dependent on the PES and be
found according to
V =
1
k (r - re ) 2
2
(4.1)
where re, V, r, and k are the equilibrium dimer bond distance, the potential energy, the
dimer bond distance, and force constant. By calculating the potential energy of as a
function of bond distance, 1.0 5.0, and taking the first derivative of equation 4.3 with
respect to r the force constant, k, was found to be 8.4 and 10.8 for silver using bulk and
cluster parameters, respectively. Also, the equilibrium bond distance, re, can be found
from taking the second derivative of equation 4.1with respect to r, which was found to be
2.55 and 2.45 for silver using bulk and cluster parameters, respectively. Figures 4.4 and
4.5 depict the potential energy curve and its derivatives used to determine r and k. These
graphs are cropped for enhanced readability of re and k.
72
30
V (eV)
20
10
2.4
2.6
2.8
3.0
3.2
3.4
r ()
(dotted line) of the potential energy curve (solid line) as well as force constant ()
determined from the second derivative (dashed line) of the potential energy curve. The
potential energy was calculated using the Sutton-Chen potential using bulk parameters.
30
V (eV)
20
10
2.4
2.6
2.8
3.0
3.2
3.4
r ()
(dotted line) of the potential energy curve (solid line) as well as force constant ()
73
determined from the second derivative (dashed line) of the potential energy curve. The
potential energy was calculated using the Sutton-Chen potential using cluster parameters.
The results for coalescence of a dimer, AB, with an atom C using the SC PES and
the cluster PES are shown in Table 4.3 for the collinear case, i.e the incident angle is
zero. When the SC PES was used for the coalescence investigations, a new dimer, BC,
was formed regardless of impact energy. Additionally, the vibrational state is mostly
independent of impact energy as the vibrational state is the same for all impact energies
with the exception of 0.1 eV and 0.2 eV. The products are quite different when the
cluster PES is used for the simulation. For example, the AB dimer is formed at energies
of 0.05 eV, 0.1 eV, and 0.4 eV while the vibrational state at 1.5 eV, 0.2 eV, and 0.5 eV in
contrast to the SC PES results. Only the products formed at 0.02 eV, 0.3 eV, 1.0 eV, and
2.0 eV are the same for both PESs.
Table 4.3. Final product(s) for the silver collinear AB + C reaction as a function of initial
kinetic energy, ET.
K(t=0)
(eV)
0.02
0.05
0.1
0.2
0.3
0.4
0.5
1.0
1.5
2.0
Bulk Sutton Chen Paramenters

AB + C
A + BC
A-B-C
X (=0)
X (=0)
X (=1)
X (=5)
X (=0)
X (=0)
X (=0)
X (=0)
X (=0)
X (=0)
Cluster Sutton Chen Parameters

AB + C
A + BC
A-B-C
X (=0)
X (=0)
X (=0)
X (=1)
X (=0)
X (=0)
X (=1)
X (=0)
X (=2)
X (=0)
74
As a further investigation into the impact of the PES on the product of the
coalescence of the 3-atom system, the incident angle was varied from 0o to 90o at impact
energies of 1.0 eV and 0.1 eV as shown in Table 4.4 and Table 4.5, respectively. Only
one case resulted in the same product and vibrational state being formed for both PESs
when the impact energy was 1.0 eV whereas none of the products were the same when
the impact energy is 0.1 eV. A triatomic complex was formed at the end of the
simulation for the SC PES at an impact energy of 0.1 eV and incident angle of 60o, and
the cluster PES produced a triatomic complex with an impact energy of 1.0 eV and an
incident angle of 45o. Although these complexes are formed during the simulation, they
may dissociate into an atom and a dimer if the simulation is run for more than 10 ps. To
determine if the trimer complex will dissociate, the simulation using the cluster PES at an
impact energy of 0.1 eV and an incident angle of 45o was run longer than 10 ps. Indeed
the triatomic complex was formed before 10 ps but dissociated into Ag2 + Ag at 65.8 ps.
Table 4.4. Final product(s) for the silver AB + C reaction with 1.0 eV of initial kinetic
energy as function of angle, .

Angle()
0
15
30
45
Bulk Sutton Chen

Paramenters
AB + C A + BC AC + B
X
(=0)
X
(=10)
X
(=16)
X
(=0)
75
Cluster Sutton Chen

Parameters
AB + C A + BC AC + B
X
(=0)
X
(=7)
X
(=0)
X
(=0)

60
X (=0)
75
X (=0)
90
X (=0)
X
(=10)
X
(=6)
X
(=7)
Table 4.5. Final Product(s) for the silver AB + C reaction with 0.1 eV of initial kinetic
energy as function of angle, .
30
Bulk Sutton Chen

Paramenters
AB + C A + BC A-B-C
X
(=1)
X
(=0)
X (=0)
45
X (=0)
Angle()
0
15
60
75
90
Cluster Sutton Chen

Parameters
AB + C A + BC AB-C
X
(=0)
X
(=0)
X
(=5)
X
X (=0)
X
(=1)
X
(=0)
X
(=0)
X
(=11)
4.3 Coalescence of Silver Clusters
Similar to the reaction pathway for the bimolecular collision shown in Figure 4.3, the
products of the bimolecular collision of Agn + Agn are either non-reactive or reactive.
However, the classification of coalescence products of Agn + Agn can be further
classified as coalescence, coalescence with scattering, and disintegration.120 Coalescence
results in the formation of a product which contains all atoms, i.e. Ag2n. Coalescence
with scattering occurs when one or more atoms are scattered from the product cluster, i.e.
76
Ag2n-S, where S in the number of scattered atoms. The third case is the complete
disintegration of the two clusters, i.e. all atoms are isolated as 2n Ag atoms.
A total of 233 trajectories were obtained from the MD simulations using the PES
derived from the cluster parameters. The analyses of these products indicate that the
products can be divided into three different cluster growth stages: nucleation mostly
non-reactive scattering products, cluster growth dominantly coalescence products, and a
transition group that is in between nucleation and cluster growth.
4.3.1 Coalescence of Ag2 + Ag, Ag2 + Ag2, Ag3 + Ag3, and Ag4 + Ag4
First, the coalescence products of Ag2 + Ag at various impact energies and

incident angles, shown in Table 4.6, are discussed. A total of 56 trajectories were
obtained for this 3-atom system, including those discussed previously in section 4.2.2.
Of these trajectories a reactive scattering product was obtained 73.5% of the time, an
elastic scattering product was obtained 21.5% of the time, and an inelastic scattering
product was formed only 5% of the time. Of the reactive scattering products, a dimer
between atoms B and C occurs most often, but a dimer between atoms A and C also
occurs at a high frequency. Interestingly, a van der Waals trimer between all three atoms
occurs at the lowest kinetic energies, 0.01 0.1 eV. At the lowest kinetic energy the
formation of a trimer complex is not dependent on angle as this product is formed at
incident angles of 0o, 30o, 60o and 90o. As the kinetic energy doubles the formation of a
trimer complex can only be found at the largest angles of 60o, 75o, and 90o. If the kinetic
energy is increased tenfold from 0.01 eV to 0.1 eV, the trimer complex is formed only at
a modest incident angle of 45o which is neither directly an atom-atom collision nor an
atom-bond collision.
The other type of reactive scattering product formed is
77
disintegration, i.e. dissociation of all three atoms. The three silver atoms are isolated
from one another with the exception of two of the atoms, which are still close enough to
form a van der Waals complex but not a bond at the end of the simulation. The threshold
energy for the dissociation of all atoms occurs at 1.5 eV. The dissociation product occurs
only at high energies of 1.5 and 2.0 eV, but is seen at angles as low as 15o and as high as
75o. Hence, the isolation of all three atoms is more sensitive to the impact energy than
the incident angle.
The incident angle has a large effect on product formation. For instance, if the
collision occurs atom-atom, =0o, a new dimer forms between atoms B and C at all
energies except at low energies of 0.01 and 0.1 eV, whereas, the collision of a silver atom
towards the center of the dimer bond, =90o, generates a range of product types which are
mostly reactive scattering products and are dependent on K (t=0). If the incident angle is
small enough so that the impact occurs mostly atom-atom a new dimer, BC, forms largely
independent of impact energy. This pattern is seen at the collinear case, =0o, and holds
true at an incident angle of 15o where most of the products are the BC dimer. However,
the frequency of the BC dimer product is only 25% when the incident angle increases to
30o. The widest variety of products occurs when the angle is 45o where the trimer and all
three possible dimers occur at different energies. Once the angle is large enough so that
the impact of atom A is directed more towards the center of the AB bond, the product is
either the AB dimer or the AC dimer in 67% of the simulations with incident angles of
60o, 75o, and 90o. Interestingly, at 75o a trimer is formed for the two lowest kinetic
energies which is then dissociated into the AC dimer as the kinetic energy increases to
0.1 eV and remains the dominant product until the kinetic energy reaches 2.0 eV, which
78
is sufficient to dissociate all atoms. When the impacting atom approaches directly
through the center of the bond of the dimer, =90o, the product is not as reactive even at
energies as high as 2.0 eV.
79
Table 4.6. The final product(s) as a function of incident angle (see Figure 1), initial internal kinetic energy, KI (t=0), final
internal kinetic energy, KI (f), and the impact energy, K (t=0) for the silver AB+C reaction. The final vibrational state is
included for dimer products, when present.
(o )
K(t=0) KI(t=0)
(eV)
(eV)
15
30
45
60
75
90
KI(f)
0.009
0.078
0.057
0.021
0.659
0.894
0.040
NA
ABC
0.009
0
AC+B
0.096
0.01
0.01
product
KI(f)
NA
ABC
0.009
0
BC+A
0.009
NA
ABC#,
0.013
0
AB+C
0.014
NA
BCA#,
0.044
0.02
0.02
0
product BC+A
KI(f)
0.01
0
BC+A
0.05
0
AB+C
0.18
0
AC+B
0.62
NA
NA
#,
CAB
ABC#
0.08
0.03
0.10*
0.07*
0
BC+A
0.13
5
BC+A
0.06
NA
CBA#,
0.15
1
BC+A
0.15
0
AC+B
0.14
0
AB+C
0.34
0.20
0.13
2
BC+A
0.26
0
AB+C
0.25
0
AB+C
0.12
1
AC+B
0.36
1
AC+B
0.27
7
AB+C
0.35
0.50
0.33
0
product AB+C
KI(f)
0.13
1
product BC+A
KI(f)
0.34
0
BC+A
5
AC+B
0
AB+C
0
AB+C
6
AC+B
7
AC+B
product BC+A
80
NA
ABC
0.03

KI(f)
1.00
0.67*
1.50
1.00
2.00
1.33
0.67
0
product BC+A
KI(f)
0.84
0.68
0.65
0.54
0.66
0.68
0.41
7
BC+A
0.42
0
BC+A
0.67
0
AC+B
1.02
10
AB+C
0.98
6
AC+B
1.03
7
BC+A
1.03
0
AB+C
0.33
5
AB+C
1.32
0
AB+C
1.34
16
AC+B
0.87
12
AC+B
0.60
NA
product BC+A BC#+A
KI(f)
1.21
1.08
0
15
7
1
0
NA
0
#
#
product BC+A
BC+A
AB +C
BC+A
AB+C
AC +B AB+C
#AC indicates a bond distance greater than 3.0 and less than 5.0 , so these atoms do not form a real bond, but
form a van der Waals complex. Denotes a triangular complex
81
To further examine product formation during the coalescence of a single atom

with a dimer we monitored the potential energy of the system as a function of simulation
time. Three trajectories were monitored at an incident angle of 0o for various impact
energies as shown in Figure 4.6 (a) (c). In Figure 4.6 (a) a vibrationally hot BC dimer
is formed within a few ps, which remains for the entire 10 ps. The oscillating pattern
seen in Figure 4.6 (a) after 2 ps is not a complete representation of BCs vibrational
motion as the data points were taken every 50 fs which is not enough time to fully reflect
a vibrational period. This pattern is also observed in other potential energy curves yet to
be discussed. In Figure 4.6 (b) a vibrationally cooler BC dimer is formed within a few
ps and again remains throughout the entire 10ps. It is obvious from the potential energy
curves of these two products that the potential energy has a greater oscillation for the
hotter BC dimer, found in Figure 4.6 (a) and reaches higher potential energies indicating
it is not as stable as the BC dimer formed in Figure 4.6 (b).
In contrast to the BC dimers formed in the above examples, an elastic product,
AB, is formed during the simulation shown in Figure 4.6 (c). The potential time curve
for this simulation paints quite a different picture than the previous two examples, where
a new dimer is formed quickly and maintained throughout the simulation. In fact, the
potential energy curve in Figure 4.6 (a) has several minima which reflect the interaction
of the three atoms throughout the entire simulation which ultimately produces an AB
dimer. The first minimum found at approximately 1000 fs is the association of the three
atoms to form an AC dimer. This dimer lasts until the three atoms again come into
contact around 4000 fs where the AB dimer is formed. The remaining minima
82
correspond to the formation of the AC and AB dimers at 5300 fs and 8000 fs,
respectively. This closer look at the potential energy indicates that a wide fluctuation in
potential energy corresponds to continued interaction of all three atoms during the
simulation whereas a relatively stable potential energy curve indicates that a dimer
quickly forms and the isolated atom no longer interacts with the dimer. Furthermore,
Figure 3.6 indicates that a trimer can be formed if excess energy is extracted from the
system within 500 fs after the start of the reaction in the cases shown in Figure 4.6 (a)
(b) but could be delayed until 8 ps for the case shown in Figure 4.6 (c).
83
-1.40
V (eV)
-1.75
-2.10
-2.45
(a)
-2.80
-1.40
V (eV)
-1.75
-2.10
-2.45
(b)
-2.80
-1.40
V (eV)
-1.75
-2.10
-2.45
(c)
-2.80
2000
4000
6000
8000
10000
Time (fs)
Figure 4.6. Potential energy, V (eV), vs. time, t (fs), for the atom-atom collision of the
three atom system, AB+C. Initial impact energy, K, is (a) 1.5 eV (b) 0.5 eV (c) 0.1 eV.
In all cases the incident angle is 0o.
84
We also examined the potential energy curves for the AB+C system at an incident
angle of 45o with varying kinetic energies, found in Figures 4.7 (a) (c). A similar
pattern to Figure 4.6 is seen in Figure 4.7. A dimer is quickly formed for Figures 4.7 (a)
and 4.7 (b) as indicated by the minimum followed by a relatively constant potential
energy for the remaining simulation time. In Figure 4.7 (c) a trimer is formed around
1000 fs as indicated by the corresponding minimum; however, the potential energy
continues to fluctuate wildly as the three atoms remain in contact but continue to
rearrange for the remaining simulation. To obtain a trimer at an incident angle of 45o
excessive energy should be removed within approximately 1.5 ps as indicated by the
results shown in Figure 4.7. The time period for energy removal is quite longer than the
collinear case shown in Figure 4.6. This increase in time for energy removal can be
understood through the partition of excess energy among the number of degrees of
freedom. For the non-collinear case, the internal kinetic energy is distributed among
three coordinates, whereas, the internal energy is distributed among two coordinates for
the collinear case. As the cluster size increases more degrees of freedom can be used to
partition the excessive energy which will result in the formation of more coalescence
products.
85
-1.0
(a)
V (eV)
-1.5
-2.0
-2.5
-3.0
-1.0
(b)
V (eV)
-1.5
-2.0
-2.5
-3.0
-1.0
(c)
V (eV)
-1.5
-2.0
-2.5
-3.0
2000
4000
6000
8000
10000
Time (fs)
Figure 4.7. Potential energy, V (eV), vs. time, t (fs), for the coalescence of the three
atom system, AB+C. Initial impact energy, K, is (a) 2.0 eV (b) 0.5 eV (c) 0.1 eV. In all
cases the incident angle is 45o.
86
The coalescence products of two dimers (Ag2 + Ag2), see Figure 2.5, as well as
K(t=0), KI(t=0), and KI(f) are shown in Figure 4.7. A non-reactive scattering product is
obtained for every case when the two dimers are initially in the same plane or parallel to
one another. This is most likely due to atoms directly colliding with one another.
However, when an atom of one dimer is directed to collide with the center of mass of the
other dimer, coalescence products are formed more often. For instance, if the dimers are
initially in the T shaped configuration a tetramer complex is formed at 0.3 eV, 0.4 eV,
and 0.55 eV. In addition to these products, the dimers exchange atoms at energies of 0.8
eV, 1.05 eV, and 1.42 eV to form two new dimers. At the highest energy, 1.9 eV, a
dimer is formed.
The remaining energies are non-reactive collisions.
Similarly,
tetratmers, non-reactive scattering, and exchanged atom dimer products are formed if the
dimers approach one another in a diamond shaped configuration.
87
of Ag2 + Ag2 as a function of initial kinetic energy. NS indicates a non-reactive

scattering product, i.e., the two original dimer clusters remain intact and Ag4 indicates a
coalescence product. The superscripts 1-4 identify the atoms, initially Ag21-2 + Ag23-4.
a) Ag2 + Ag2: initially facing each other
K (t=0)
(eV)
0.3
KI (t=0)
(eV)
0.15 0.20 0.25 0.27 0.30 0.33 0.5
KI (f)
(eV)
0.8
0.85 0.95 1.05
1.42
1.9
0.40
0.42 0.47 0.52
0.71
0.95
0.15 0.18 0.25 0.18 0.11 0.18 0.20 0.37
0.29 0.45 0.45
0.62
0.91
NS
NS
Product NS
0.4
NS
0.5
NS
0.55 0.6
NS
NS
0.65 0.7
NS
NS
NS
NS
NS
NS
0.65 0.7
0.8
0.85 0.95 1.05
1.42
1.9
b) Ag2 + Ag2: initially side by side

K (t=0)
(eV)
0.3
KI (t=0)
(eV)
0.15 0.20 0.25 0.27 0.30 0.33 0.5
0.40
0.42 0.47 0.52
0.71
0.95
KI(f)
(eV)
0.14 0.19 0.15 0.23 0.23 0.16 0.27 0.35
0.43 0.37 0.53
0.72
0.93
NS
NS
Product NS
0.4
NS
0.5
NS
0.55 0.6
NS
NS
NS
NS
NS
NS
NS
NS
0.65 0.7
0.8
0.85 0.95 1.05
1.42
1.9
c) Ag2 + Ag2: initially T shaped

K (t=0)
(eV)
0.3
KI (t=0)
(eV)
0.15 0.20 0.25 0.27 0.30 0.32 0.35 0.40
0.42 0.47 0.52
0.71
0.95
KI(f)
(eV)
0.81 0.65 0.21 0.24 0.25 0.16 0.35 0.38
0.41 0.26 0.23
0.32
0.30
Product Ag4
0.4
Ag4
0.5
NS
0.55 0.6
Ag4
NS
NS
88
NS
Ag21,3 NS
Ag22,4
NS
Ag21,3 Ag21,3 Ag3+Ag

Ag22,4 Ag22,4

D) Ag2 + Ag2: initially Diamond shaped
K (t=0)
(eV)
0.3
KI (t=0)
(eV)
0.15 0.20
KI(f)
(eV)
0.83 0.13
Product Ag4
0.4
0.5
0.8
0.85 0.95 1.05
1.42
1.9
0.25 0.27 0.30 0.32 0.35
0.40
0.42 0.47 0.52
0.71
0.95
0.23 0.25 0.11 0.33 0.21
0.30
0.24 0.47 0.52
0.70
0.40
Ag21,3 NS
Ag22,4
0.55 0.6
Ag4
NS
0.65 0.7
NS
Ag21,3 Ag21,3 NS
Ag22,4 Ag22,4
*Table 4.7 sections (a-d) correspond to Figure 2.5 (a,-d).
89
NS
Ag21,3 Ag21,3 Ag21,3

Ag22,4 Ag22,4 Ag22,4
Increasing the size of the colliding clusters to three atoms, see Figure 2.5, results
in the formation of hexamer coalescence products at K(t=0) = 0.3 eV, 0.5 eV, 0.55 eV,
0.6 eV, 0.65 eV and 1.05 eV for the collision of the planar trimers as shown in Table 4.8
However, when the trimers are initially in the linear configuration non-reactive scattering
products are formed at all energies. Similar to the coalescence products seen at a
colliding cluster size of two and three atoms, the collision of two tetramers does not result
in a large number of coalescence products. A potential energy analysis was completed,
as shown in Figure 4.8, to monitor the fluctuation of potential energy vs. time for two
trajectories of the coalescence of Ag3 + Ag3. In the top picture Ag6 is formed at K(t=0) =
1.05 eV. In this case the potential energy quickly reaches a minimum, remains constant
with oscillation, and is smaller than the initial potential at the end of the simulation.
However, the bottom picture of Figure 4.8 tells a different story. This potential energy
curve is at impact energy of 1.42 eV and the formation of a coalescence cluster occurs,
but quickly dissociates into the two original trimers. During this process the potential
energy oscillates widely throughout the simulation, reaching a minimum around 7 ps and
increasing dramatically after that time. In fact the potential energy is above the initial
potential energy for most of the simulation and at a greater magnitude than the energy
profile, previously discussed for the 3-atom system. In order to isolate the cluster formed
early in the simulation, energy would need to be removed from the system to cool the
cluster.
90

scattering product, i.e., two original trimer clusters remain intact and Ag6 indicates a
coalescence product.
a) Ag3 + Ag3: planar structure in same plane
K (t=0)
(eV)
0.3
0.4
0.5
0.55
0.6
0.65
0.7
0.8
0.85
0.95
1.05
1.42
1.9
KI (t=0)
(eV)
0.15
0.20
0.25
0.27
0.30
0.33
0.35
0.40
0.42
0.47
0.52
0.71
0.95
KI (f)
(eV)
0.59
0.08
0.62
0.59
0.21
0.26
0.13
0.24
0.21
0.43
0.13
0.42
0.42
NS
Ag6
Ag6
Ag6
Ag6
NS
NS
NS
NS
Ag6
NS
NS
Product Ag6
b) Ag3 + Ag3: linear structure in same plane

K (t=0)
(eV)
0.3
0.4
0.5
0.55
0.6
0.65
0.7
0.8
0.85
0.95
1.05
1.42
1.9
KI (t=0)
(eV)
0.15
0.20
0.25
0.27
0.30
0.33
0.35
0.40
0.42
0.47
0.52
0.71
0.95
KI (f)
(eV)
0.46
0.26
0.27
1.07
0.45
0.38
0.36
0.60
0.40
0.30
0.16
0.72
0.95
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
Product NS
*Table 4.8 sections (a,b) correspond to Figure 2.5(e,f).
91
-5.4
-5.7
V (eV)
-6.0
-6.3
-6.6
-6.9
-5.4
-5.7
V (eV)
-6.0
-6.3
-6.6
-6.9
7500
15000
22500
30000
37500
Time (fs)
Figure 4.8. Potential energy, V (eV), vs. time, t (fs), for the coalescence of Ag3 + Ag3.
Initial impact energy, K, is (a) 1.05 eV (b) 1.42 eV. Both cases are the planar trimer in
the same plane, as shown in Figure 1(c).
92
The coalescence products, i.e. Ag8, for the tetramer collisions, see Figure 2.5, were
seen at K(t=0) = 0.3 eV, 0.55 eV, 0.6 eV, 0.85 eV, and 0.95 eV as shown in Table 4.9.
Of those energies the formation of a coalescence product was also seen at 0.3 eV, 0.55
eV, and 0.60 eV for the trimers. The snapshots of the coalescence products from these
energies are shown in Figure 4.9 (a) (f). These Ag8 structures consist of significant
triangular units that are the building blocks of silver clusters as discussed in Chapter 3.
Also, in comparison to the coalescence of Ir4 + Ir4, where only coalescence products, i.e.
Ir8, were formed within the same kinetic energy range, the coalescence mechanism of
Ag4 + Ag4 is quite different.
All of the results from the four systems discussed, i.e. Ag2 + Ag, Ag2 + Ag2, and Ag3
+ Ag3, indicate that the coalescence of these systems is at the nucleation stage. For
example, in order to form coalescence products, energy would need to be removed from
the system to prevent the products of becoming non-reactive or other types of reactive
products. The results shown in Figures 4.6 4.8 also demonstrate that timing for
excessive heat removal after the collision is critical and depends on the kinetic energy,
incident angles, and the size of the system. For instance, comparison between Figure 4.6
and 4.8 illustrates that as the size of the system increases the excessive kinetic energy can
be removed at a later time after collision.
93

scattering product, i.e., the two original tetramer clusters remain intact and Ag8 indicates
a coalescence product.
a) Ag4 + Ag4: two tetramers initially in same plane
K (t=0)
(eV)
0.3
0.4
0.5
0.55
0.6
0.65
0.7
0.8
0.85
0.95
1.05
1.42
1.9
KI (t=0)
(eV)
0.15
0.20
0.25
0.28
0.30
0.33
0.35
0.40
0.43
0.48
0.53
0.71
0.95
KI (f)
(eV)
0.69
0.12
0.11
0.56
0.36
0.36
0.20
0.34
0.64
0.78
0.31
0.45
0.68
Product
Ag8
NS
NS
Ag8
Ag8
NS
NS
NS
Ag8
Ag8
NS
NS
NS
b) Ag4 + Ag4: two tetramers initially parallel

K (t=0)
(eV)
0.3
0.4
0.5
0.55
0.6
0.65
0.7
0.8
0.85
0.95
1.05
1.42
1.9
KI (t=0)
(eV)
0.15
0.20
0.25
0.28
0.30
0.33
0.35
0.40
0.43
0.48
0.53
0.71
0.95
KI (f)
(eV)
0.32
0.35
0.29
0.73
0.76
0.44
0.90
0.52
0.61
0.32
1.21
0.78
0.98
Product
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
Ag8
NS
NS
*Table 4.9 sections (a,b) correspond to Figure 2.5(g,h).
94
0.30 eVSP
0.55 eVSP
0.60 eVSP
0.85 eVSP
0.95 eVSP
1.05 eVPA
of two tetramers. The initial impact kinetic energy and initial cluster orientation is given
for each.
SP
denotes an initial orientation with the two clusters in the same plane.
PA
denotes an initial orientation with the two clusters parallel to one another
4.3.2
Coalescence of Ag5 + Ag5 and Ag6 + Ag6
In contrast to the trimers and the tetramers, the collision of two pentamers, see Figure
2.5, in the same plane results in the formation of coalescence products, i.e. Ag10 for all
energies study as shown in Table 4.10. The initial cluster orientation has a profound
impact on the type of coalescence products formed. For instance, the products obtained
from the Ag5 + Ag5 reaction for two different starting arrangements, i.e. in the same plane
and parallel, are listed in Table 4.10 and have dramatically different results. Two
different products were obtained for the different configurations; the same plane
configuration resulted in coalescence, i.e. Ag10, for all energies while the parallel
configuration resulted in non-reactive scattering for all energies. The difference in the
product formation based upon the initial geometry configuration is not completely
95
surprising. When the two pentamers are facing each other, i.e. an atom atom collision,
there is more repulsion between all ten atoms as the two pentamers approach one another.
However, when the two pentamers are in the same plane the repulsion between atoms is
less as they approach one another as only two atoms are overlapping. This pattern is also
seen for the different configurations of dimers, trimers, tetramers and hexamers, with a
few exceptions for each cluster size. Another explanation for the difference in product
formation for parallel configurations versus same plane configurations is the number of
degrees of freedom involved in the kinetic energy partition. The number of degrees of
freedom is the same for both configurations, but the parallel configuration makes the
energy transfer among the different modes more difficult.
Snapshots for the products from the collision of two pentamers are shown in Figure
4.10. The decamer product for the collision of two pentamers at energy of 0.70 eV,
shown in Figure 4.10, is very interesting as it appears that the product could easily be
composed of a complex between a planar trimer and a planar heptamer. Interestingly,
this planar trimer and heptamer are similar to the most stable geometries found from our
DFT studies for their corresponding cluster sizes. Hence, we examined if the decamer
product would separate into these two structures if the simulation were run longer than 40
ps. We doubled the simulation time, but the decamer remained intact, as shown in Figure
4.10, and rearranged to form more bonds between the atoms indicating a more stable
complex.
96

scattering product, i.e., the two original pentamer clusters remain intact and Ag10
indicates a coalescence product.
a) Ag5 + Ag5: two pentamers initially in same plane
K (t=0)
(eV)
0.3
0.4
0.5
0.55
0.6
0.65
0.7
0.8
0.85
0.95
1.05
1.42
1.9
KI (t=0)
(eV)
0.15
0.20
0.25
0.27
0.30
0.32
0.35
0.40
0.42
0.47
0.52
0.71
0.95
KI (f)
(eV)
0.77
0.59
0.63
0.98
0.65
0.72
0.53
0.71
0.65
0.98
0.63
0.59
0.77
Product
Ag10
Ag10
Ag10
Ag10
Ag10
Ag10
Ag10
Ag10
Ag10
Ag10
Ag10
Ag10
Ag10
b) Ag5 + Ag5: two pentamers initially parallel

K (t=0)
(eV)
0.3
0.4
0.5
0.55
0.6
0.65
0.7
0.8
0.85
0.95
1.05
1.42
1.9
KI (t=0)
(eV)
0.15
0.20
0.25
0.27
0.30
0.32
0.35
0.40
0.42
0.47
0.52
0.71
0.95
KI (f)
(eV)
1.02
1.68
1.45
0.97
1.12
0.79
0.89
0.93
0.73
0.74
1.06
1.03
1.33
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
Product
*Table 4.10 sections (a,b) correspond to Figure 2.5(i,j).
97
0.70 eV#,SP
0.70A eV#,SP
1.90 eV,SP
0.05 eV,PA
1.05 eV*
1.42 eV
of #Ag5 + Ag5, Ag6 + Ag6, *Ag7 + Ag7, and Ag8 + Ag8. The initial impact kinetic
energy and initial cluster orientation is given for each.
denotes a total simulation time
of 80 ps. SP denotes an initial orientation with the two clusters in the same plane.
PA
denotes an initial orientation with the two clusters parallel to one another
The products for the collision of Ag6 + Ag6, see Figure 2.5, are shown in Table 4.11.
Hexamers colliding within the same plane also form a coalescence product at all energies
however, at the highest kinetic energy coalescence with scattering is seen as the products
are a silver trimer and nonamer. In addition, coalescence products are formed when the
hexamers are initially parallel to one another when the impact energy is small. This
indicates that the cluster growth stage becomes dominant in coalescence of 12-atom
98
systems. In Figure 7 snapshots are given for the Ag6 + Ag6 collison at different energies.
Due to the excessive internal kinetic energy, both structures are far from the global
energy minimum.
The coalescence products from the 10 and 12 atom collisions result in more
coalescence products as compared to the products form in section 4.3.1. This change
represents a transition from nucleation to a cluster growth mechanism.
Despite the findings that the cluster size and orientation play a key role in
determining the growth process, i.e. nucleation or cluster growth, the initial kinetic
energy also plays an important role in determining whether the process is nucleation or
cluster growth. For example, for certain energies for the collision of the dimers in the T
shape, dimers in the diamond configuration, the planar trimers, and the tetramers
colliding in the same plane, a coalescence product was formed while the remaining
energies resulted in non-reactive scattering.
99

scattering product, i.e., the two original hexamer clusters remain intact and Ag12 indicates
a coalescence product. The superscripts 1-12 identify the atoms, initially Ag61-6 + Ag6712
a) Ag6 + Ag6: two hexamers initially in same plane

K (t=0)
(eV)
0.3
0.4
0.5
0.55
0.6
0.65
0.7
0.8
0.85
0.95
1.05
1.42
1.9
KI (t=0)
(eV)
0.15
0.20
0.25
0.27
0.30
0.32
0.35
0.40
0.42
0.47
0.52
0.71
0.95
KI (f)
(eV)
1.79
0.62
0.56
0.86
0.96
0.96
1.01
0.68
0.85
0.75
0.89
1.31
0.81
Product
Ag12
Ag12
Ag12
Ag12 Ag12
Ag12
Ag12
Ag12
Ag12
Ag12
Ag12
Ag12 Ag91-7,1112
Ag38-10
b) Ag6 + Ag6: two hexamers initially parallel
K (t=0)
(eV)
0.3
0.4
0.5
0.55
0.6
0.65
0.7
0.8
0.85
0.95
1.05
1.42
1.9
KI (t=0)
(eV)
0.15
0.20
0.25
0.27
0.30
0.32
0.35
0.40
0.42
0.47
0.52
0.71
0.95
KI (f)
(eV)
0.60
2.58
1.81
1.90
0.86
1.12
0.85
1.26
1.00
1.03
1.11
1.31
1.49
Product
Ag12
Ag12
Ag12
Ag12 NS
NS
NS
NS
NS
NS
NS
NS
*Table 4.11 sections (a,b) correspond to Figure 2.5(k,l).
100
NS
4.3.3 Coalescence of Ag7 + Ag7, Ag8 + Ag8, and Ag19 + Ag19
The reactions Ag7 + Ag7 and Ag8 + Ag8, see Figure 2.5, are shown in Tables 4.12 and
4.13, respectively. The collision of hepatmers forms a coalescence product, Ag14, at all
energies with one exception. This occurs when two heptamers collide at energy of 1.05
eV and a single atom is ejected from the complex, i.e. Ag13 is formed, which is shown in
Figure 4.10. For the octamers a coalescence product, Ag16, occurs at all energies. A
snapshot of one these products is shown in Figure 4.10. These results indicate that the
cluster growth stage is dominant for Agn + Agn coalescence with n 7 atoms.
101

a) Ag7 + Ag7: two heptamers
K (t=0)
(eV)
0.3
0.4
0.5
0.55
0.6
0.65
0.7
0.8
0.85
0.95
1.05
1.42
1.9
KI (t=0)
(eV)
0.15
0.20
0.25
0.27
0.30
0.32
0.35
0.40
0.42
0.47
0.52
0.71
0.95
KI (f)
(eV)
0.98
1.14
0.94
0.82
0.86
0.89
1.48
1.01
1.26
1.05
0.93
1.22
1.26
Product Ag14 Ag14 Ag14
Ag14 Ag14 Ag14 Ag14 Ag14 Ag14 Ag14
Ag1313,5-14
Ag14 Ag14
Ag4
*Table 4.12 section (a) corresponds to Figure 2.5(m).

a) Ag8 + Ag8: two octamers
K (t=0)
(eV)
0.3
0.4
0.5
0.55
0.6
0.65
0.7
0.8
0.85
0.95
1.05
1.42
1.9
KI (t=0)
(eV)
0.15
0.20
0.25
0.27
0.30
0.32
0.35
0.40
0.42
0.47
0.52
0.71
0.95
KI (f)
(eV)
1.17
1.44
1.56
1.06
1.07
1.26
0.99
1.40
1.08
1.65
1.89
2.10
1.71
Product Ag16 Ag16
Ag16
Ag16 Ag16 Ag16 Ag16
*Table 4.13 section (a) correspond to Figure 2.5(n).
102
Ag16 Ag16 Ag16 Ag16 Ag16 Ag16
The last study of silver coalescence was of two Ag19 + Ag19 as shown in Table
4.14. Clusters of thirty-eight atoms are extremely interesting because this is a
geometrical magic size.123 At 38 atoms there is the correct number of atoms to form a
highly symmetric piece of fcc bulk matter, the perfect truncated octahedron. Silver
clusters and copper clusters of 38 atoms have also shown to be a magic size by Doye and
co-workers. Hence, it may be interesting to examine the coalescence of two 19 atom
clusters to see if they form the energetically magic truncated octahedron. Table 4.14 lists
the five initial impact energies, K (t=0), initial internal kinetic energy, KI (t=0), final
internal kinetic energy, KI (f), and product formed. Besides the study of impact energy
dependence on cluster formation, the incident angle was also varied from zero to fortyfive degrees, see Figure 2.5. The product formed for all energies and at incident angles
smaller than 60o is indeed a 38 atom cluster; selected snapshots are shown in Figures 4.11
and 4.12. When the incident angle is zero or thirty degrees the clusters interact at many
points of contact, however, when the incident angle increase to 30o the two clusters only
interact at a few points. Although a coalescence product is formed in every case, i.e
Ag38, the product never corresponds to a truncated octahedron. In fact the structures
formed are of low-symmetry, which is due to the systems large kinetic energy, or
temperature, at the end of the simulation time. Hence, to get a better idea if the
coalescence could form a truncated octahedron the kinetic energy would need to be
removed from the system to cool off the clusters and allow the structures to relax to the
global minimum.
103

scattering product, i.e., two original Ag19 clusters remain intact and Ag38 indicates a
coalescence product.
(a) Ag19 + Ag19
K(t=0) KI(t=0)
(eV)
(eV)
(o )
0
30
45
KI(f)
1.78
3.21
1.73
product Ag38
Ag38
Ag38
KI(f)
2.51
1.57
2.63
1.42
0.71
product Ag38
Ag38
Ag38
KI(f)
1.90
1.99
1.98
1.90
0.95
product Ag38
Ag38
Ag38
KI(f)
3.65
2.73
2.37
3.80
1.90
product Ag38
Ag38
Ag38
KI(f)
3.61
4.68
3.40
5.70
2.90
product Ag38
Ag38
Ag38
*Table 4.14 section (a) corresponds to Figure 2.5(o).
0.95
0.95 eV
0.48
1.42 eV
104
60
1.01
NS
1.24
NS
1.47
NS
2.39
NS
3.38
NS
1.90 eV
of Ag19 + Ag19. The initial impact kinetic energy is given for each snapshot. The
incident angle is 0o for each simulation.
0o
30o
45o
of Ag19 + Ag19. The incident angle is given for each snapshot. The initial impact energy
is 0.95 eV for each simulation.
4.4 Summary
The binding energy obtained from the original SC potential was compared to our
DFT results for the silver dimers and the trimers. It was found that the original SC
potential was not accurate for describing small metal clusters, which is not surprising as
the SC potential parameters were optimized to silvers bulk properties. We optimized
these parameters to the DFT results discussed in Chapter 3 and constructed a new PES
for silver. MD simulations were performed using the bulk and cluster PESs to study the
coalescence of a 3-atom system, AB + C. This reaction was investigated with various
105
incident angles and initial kinetic energies. The MD results demonstrated that the
accuracy of a PES is critical to the outcome of the dynamic simulations. The MD results
also show that the products of coalescence were greatly influences by both the incident
angle and the energy.
MD using the cluster SC potential were completed for Ag2 + Ag and Agn + Agn (n
= 2 8 , 19). The three-atom system revealed that product formation was sensitive to the
incident angle and at certain energies all three atoms were dissociated. A trimer complex
is easily formed between all three atoms when the impact energy is below 0.1 eV. An
atom to atom collision leads to the formation of a new dimer for energies larger than
K(t=0) = 0.3 eV. The Agn + Agn (n = 2 8, 19) studies revealed that nucleation is
dominant for the coalescence of systems containing eight or less Ag atoms while the
cluster growth is dominant in the coalescence of the systems 14 or more Ag atoms. The
removal of excessive energy is critical for the rare formation of Ag clusters when the
collision occurs between two clusters smaller than six atoms.
The excessive energy observed in the silver coalescence systems studied in this
chapter is critical for cluster growth at small sizes, various geometry orientations, and
high impact kinetic energy. Removing this energy using a carrier gas or thermostat
would allow the coalescence products to relax to the global minimum. Therefore, MD
simulations at a constant temperature, i.e. removal of excessive kinetic energy, should be
studied.
Ostwald ripening is another interesting process for cluster growth; therefore, the MD
simulations of an Ostwald ripening growth process for small silver clusters would be
106
extremely beneficial; particularly when they are compared with the diffusion based
coalescence reactions discussed in this chapter.
The coalescence of other structures, i.e. nanowires and nanotubes, would be very
interesting as well.
107
CHAPTER 5
SYNTHESIS AND CHARACTERIZATION OF AgS, NiS, AND HgSe
5.1 Motivation and Background
The ability to predict and control the size and shape of metal and semiconductor
nanoparticles is crucial to the manipulation of the nanoparticles electronic and magnetic
properties for application purposes. Different synthetic routes have been successful in
producing a variety of materials ranging from nanorods, nanodisks, to nanofibers, just to
name a few. 13,14,31-33,58,77,124-135 Metal and semiconductor nanoparticles are formed using
different synthetic routes: unsupported in the liquid phase, i.e. colloidal solution
synthesis,28-32,125,126,130 and gas phase preparations33 or supported on solid
substrates108,117,155-157. The gas phase preparation of clusters ordinarily includes the
formation of metal atoms by the decomposition of precursor gases, by sputtering or laser
abalation.28,33
Typically, in the liquid phase preparation of nanoparticles, clusters are formed
from the reduction reaction of a precursor28,32,130, often with the addition of ligands to
passivate the cluster surface.107,125,158 Colloidal synthesis of naked, or unprotected,
semiconductor nanoparticles are typically unstable, particularly, when solvent is
removed. Hence, ligands are introduced into the synthetic method to increase the long
term stability of the semiconductor clusters in dry and wet systems. More importantly,
colloidal synthetic methods that employ organic monolayers to protect the cluster surface
can be exploited to manipulate the size and shape of nanoparticles by varying the feed
ratios of reactants, reaction time, and the reaction temperature.40,44,48,137,138,143,144,154,159
Furthermore, the monolayer protected clusters (MPCs) can be manipulated at any time,
108
even after the synthesis is complete, by surface exchange or surface coupling reactions of
the protective ligands. The manipulation of these protective ligands affects not only the
chemical functionalities and stability of the MPCs, but also affects the electronic
properties of the MPCs. The electronic properties of interest are the photochemical
characteristics, i.e. the optical absorption and photoluminescence, and electrochemical
characteristics, i.e. the electronic conductivity and non-aqueous phase electrochemistry.
In addition to the sensitivity of electronic properties of metal and semiconductor
nanoparticles to size, shape, and synthetic protocols, the electronic properties of metal
and semiconductor nanoparticles can be affected by organizing MPCs ino assemblies.160163
For instance, the ordering and distribution of the nanoparticles can play an important
role in regulating the properties of the overall assemblies.160,164 The creation of nanoarchitectures and assemblies is critical for the fabrication of novel electronic nanodevices
and nanocircuits, hence, it is vital to explore the influence of size and shape on the
electronic properties of MPCs as well as the corresponding electronic properties of these
MPCs in organized assemblies. The effect of organizing MPCs into a monolayer
assembly on the air/water interface using the Langmuir-Blodgett technique has been
explored for Au, Ag, PbS, and CdTe nanoparticles.160,163,165 These studies illustrated that
the interparticle spacing played a crucial role in determining the electronic conductivity
and optical properties of nanoparticle ensembles.160,163,165 For instance, Greene and coworkers demonstrated that the band gap of CdTe MPCs red shifted as the interparticle
spacing was decreased.
We chose to investigate a solution-based approach to the synthesis of HgSe, AgS,
and NiS nanoparticles passivated by a monolayer of alkanethiolates. In addition, UV-
109
Vis, fluorescence, and electrochemical studies were carried for these MPCs. It is also our
intention to produce semiconductor MPCs that can be organized into a LB monolayer for
electronic conductivity studies.
5.2 NiS
5.2.1 Room Temperature, Liquid Synthesis of NiS Nanoparticles
5.2.1.1 Synthesis
The size and shape dispersity of semiconductor nanoparticles have been found to
be dependent on the feed ratio of the reactants for the synthesis of semiconductor
nanoparticles.44 Hence, it is vital to explore the effects of varying the ratio of Ni(Ac)2 to
hexanethiol and sodium sulfide. Also, the overall particle sizes of naked semiconductor
nanoparticles have been shown to increase with reaction time, which indicates that
studying the growth dynamics of monolayer protected nanoparticles is critical to
understanding the synthesis of NiS nanoparticles of varying sizes and shapes in a
controllable manner.9 Therefore, it is important to study the growth dynamics of
monolayer protected nanoparticles as a function of reaction time. Besides the feed ratio
of reactants and reaction time, the length of the alkane chain in the alkanethiolate may
influence the size and shape of nanoparticles. For instance, longer alkane chains in the
alkanethiols have more interligand interactions, which provide a greater stability and
ordering to the monolayers adsorbed onto the gold clusters; hence, it is more difficult for
the S2- ions to displace the longer chained alkanethiol ligands. The nanoparticle size is
determined by the ability of S2- displace the alkanethiols and cluster neighboring nickel
atoms together to form larger particles. To study this effect the chain length of the
protecting ligand was increased from six carbon atoms to 12 carbon atoms. The NiS
110
nanoparticles were synthesized according to the procedure described in Chapter 2. First,

the growth dynamics of the nanoparticles as a function of reaction time are discussed,
followed by the discussion of the effect of the feed ratio of Ni(Ac)2 to alkanethiolate, and
the effect of the feed ratio of Ni(Ac)2 to Na2S.
5.2.1.1.1 Nanoparticle Growth Damics
The NiS nanoparticle growth was monitored using UV-Vis spectroscopy.

Aliquots of the stirring NiS reactants were taken for UV-Vis measurement at different
time intervals after the addition of Na2S and compared to the NiS reaction prior to the
addition of Na2S as shown in Figure 5.1. This dynamic study provides important
information about the dependence of particle concentration and size on the reaction time.
The absorption profile shows an exponential decay and two large absorption peaks with a
shoulder leading to lower energies, regardless of reaction time. The first peak is a sharp
peak located at 338 nm corresponding to 3.7 eV. Notice that as time increases the
absorbance maximum of this first peak steadily increases until a steady state is reached
two hours and twenty minutes after the addition of sodium sulfide, as indicated by the
plotting of peak intensity as a function of time shown in Figure 5.2.
The second peak is broader and less intense than the first peak and is located at
420 nm which is roughly 2.96 eV. Immediately following the addition of the sodium
sulfide, i.e. time = 0, peak two has the highest absorbance, but as time goes on this the
absorption intensity of this peak decreases and is accompanied with a corresponding blue
shift. The third peak is located at 526 nm, i.e. 2.4eV, is very broad. Similar to the peak
located at 420 nm, the third peak at 526 nm decreases in intensity.
111
3.5
Before
0min
20min
40min
60min
80min
110min
140min
200min
260min
320min
1day
2day
3days
3.0
Absorbance
2.5
340
2.0
1.5
420
1.0
526
0.5
0.0
-0.5
100
200
300
400
500
600
700
800
900
1000
(nm)
Figure 5.1. The UV-Vis profile of C6-NiS (rt, 3X, 0.1X). Each UV-Vis profile was taken
before the addition of Na2S and at various time intervals after the addition of Na2S.
Absorbance Peak Intensity
2.4
2.2
2.0
1.8
340
420
1.6
1.4
1.2
1.0
0.8
0.6
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
Time (minutes)
Figure 5.2. Variation of the UV-Vis peak intensity of the C6-NiS (rt, 3X, 0.1X) with
reaction time before and after the addition of Na2S.
112
5.2.1.1.2 Effect of Feed Ratio of Ni(Ac)2 to C6H13SH
The reaction to form NiS nanoparticles is similar to the synthesis of alkanthiolate

protected PbS nanoparticles.44 For instance, the addition of the alkanethiol creates a [NiS(R)-]n polymer, but after the addition of Na2S the alkanethiol is displaced by the S2ions. This displacement causes the neighboring nickel ions to cluster together and form
the NiS nanoparticles. The first synthesis was that of C6-NiS (rt, 1x, 0.1); the solution
color changed from a teal blue to a dark brown after the addition of 1-hexanethiolate.
After addition of the Na2S the solution color changed only slightly to a reddish brown,
which was not a significant color change, but the solution was already substantially dark
after the addition of 1-hexanethiolate. The color change in the reaction indicated that
nanoparticles were indeed formed, however upon the addition of water to initiate phase
transfer the color of the toluene phase changed from brown to clear. Subsequently, the
water phase turned a cloudy brown, which indicated that the nanoparticles were
transferred from the toluene phase to the water phase. The loss of particles to the water
phase suggests that the particles were very hydrophilic which could have been due to an
insufficient surface coverage of alkanethiol; hence, the ratio of alkanethiol to the nickel
salt was increased to a fourfold excess. Another explanation for the loss of product to the
water phase is that nanoparticles were not formed as alkanethiolate protected
nanoparticles are not soluble in water.
The synthesized C6-NiS (rt, 4x, 0.1) exhibited the same color change as the C6NiS (rt, 1x, 0.1), but these nanoparticles were not transferred to the water phase during
the phase separation step. However, after the removal of the toluene the particles were
113
found to be very sticky and were transferred to the frit as one large oily ball. During the
purification of the nanoparticles, i.e. rinsing the nanoparticles with methanol, the oily ball
dissolved in methanol, which resulted in the transfer of the nanoparticles through the frit
to the waste collection flask. The solubility of C6-NiS (rt, 4x, 0.1) in methanol can be
explained by the excess alkanethiol in solution. This excess alkanethiol acts like a
solvent, which dissolved the nanoparticles. The next ratio was C6-NiS(rt, 2x, 0.1) and
C6-NiS(rt, 3x, 0.1) which were made and purified successfully. These nanoparticles were
still very oily, which resulted in a lengthy filtering step.
5.2.1.1.3 Effect of Feed Ratio of Ni(Ac)2 to Na2S
Next, the ratio of sodium sulfide to nickel acetate was varied. A series of
particles were made beginning with C6-NiS (rt, 2x, 0.1x) and followed by the increase of
sodium sulfide by 0.1 mmole. During the synthesis and purification steps of C6-NiS (rt,
2x, 0.1 0.3x ) the solution appeared to have little difference until the sodium sulfide
ratio was increased to 0.4 mmole. The C6-NiS (rt, 2x, 0.4x) yielded a solution that was
not sticky as the previous three batches of nanoparticles synthesized, i.e. C6-NiS (rt, 2x,
0.1 0.3x). The nanoparticles were not dissolved in methanol during the purification
process and were flaky when scraped off the wall of the round bottom flask with a
spatula. This is an indication that the particles were not being dissolved by excess thiol
and had sufficient alkanethiol coverage. The resulting uv-vis profile was radically
different and will be discussed later. So, ratios of sodium sulfide which were 0.3 times
more than the nickel acetate produced successful results.
5.2.1.1.4 Effect of the Purification Process
114
The last change made to the synthetic protocol was the purification and collection
steps. Because some of the products synthesized were oily or soluble in methanol, new
strategies were used in the purification process. The excess alkanethiol in the sample was
very difficult to remove, so three different strategies were employed either alone or in
combination: extensive periods of solvent removal on a rotary evaporator, a
solvent/nonsolvent scheme, and a precipitation route. Extensive periods on the
evaporator resulted in a decrease of the nanoparticles solubility in methanol because
some of the solvent was removed. However, the alkanethiol can not be removed.
The second strategy used a solvent/nonsolvent route, which involved the
dispersion of the nanoparticles in hexanes and subsequent washings of methanol.
Methanol and hexanes are slightly miscible, but will easily phase separate. The idea
behind this approach is that the nanoparticles will be soluble in hexane and the excess
alkanethiol will be soluble in the methanol layer. Hence, upon vigorous stirring for a
short period of time, followed by the cessation of stirring to allow the solution to phase
separate, the nanoparticles will diffuse to the hexane layer and the alkanethiol will diffuse
to the methanol layer. Then the methanol can then be easily removed using a pipet,
which also removes the excess alkanethiol. The disadvantage to this method is that it
takes several hours and must be repeated at least four times to be successful.
The third isolation method used was to dry the nanoparticles, add methanol to the
flask, and scrap the oily nanoparticles away from the side of the flask with a spatula to
disperse them into the methanol. The flask was then placed in the freezer for several
hours to precipitate the alkanethiol for removal. However, when this method was used
the alkanethiol did not precipitate and the particles were still were soluble in the
115
methanol. The best results for nanoparticles purification were achieved using a
combination of the solvent/nonsolvent & extensive evaporation methods.
5.2.1.2 UV-Vis of NiS Nanoparticles
The Uv-Vis measurements were taken on the above samples to probe the
electronic structure of the nanoparticles. Figure 5.3 shows the absorption profile of C6NiS nanoparticles synthesized with various sodium sulfide ratios. All four samples show
the same peaks with only a slight decrease in intensity when the Na2S ratio is larger than
0.1 x. This indicates that the Na2S ratio doesnt have an affect on the size of the NiS
nanoparticles as there is a lack of shift in the UV-Vis spectra or that nanoparticles were
never formed during the synthesis.
1.4
1.2
Absorbance
1.0
(rt, 2x, 0.4)
(rt, 2x, 0.3)
(rt, 2x, 0.2)
(rt, 2x, 0.1)
0.8
0.6
0.4
0.2
0.0
200
300
400
500
600
700
800
900
(nm)
Figure 5.3. UV-Vis spectra of the C6-NiS particles synthesized under various conditions.
The particles were dissolved in chloroform at a concentration of 0.033 mg/mL.
116
The optical spectra of C6-NiS nanoparticles are shown in Figure 5.4 for different feed
ratios of alkanethiol, 2x and 3x. Three peaks are observed for both samples of C6-NiS at
340 nm, 420 nm, and 526 nm for the C6-NiS (rt, 2x, 0.1x) and 337 nm, 420 nm, and 590
nm for the C6-NiS (rt, 3x, 0.1x). The exact peak position is determined by the second
derivative of the UV-Vis spectra. Both samples exhibit a peak around 340 nm and 420
nm, but the last peak at 526 nm red-shifts to 590 nm as the alkanethiol is increased. The
corresponding energies to these peaks are given in Figure 5.4 and could correspond to a
band gap energy for C6-NiS (rt, 2x, 0.1x) and for C6-NiS (rt, 3x, 0.1x). Both of these
energies are much larger than the bulk band gap of NiS which was been found to have an
energy of 0.14 eV166,167, although the authors concede that it is possible for the band gap
energy of NiS to lie in the range of 0.14 eV 0.40 eV. In fact, Nakamura found the
band-gap energy for bulk NiS as high as 2.1 eV.168 Regardless of peak assignment, the
increase in band gap energy is a direct indication that the size of these particles are much
smaller than the bulk NiS nanoparticles. These peaks could arise from the NiS
nanoparticles or Ni(II) complexes. By comparing with the fluorescence data to be
discussed in more detail later, the peak located at 3.65 and 3.67 eV can be assigned to the
first excitonic peak of the NiS nanoparticles. This energy is 1.5 eV higher than the bulk
NiS band gap energy, which is an indication that the size of these nanoparticles is very
small. Also, the increase of band gap energy for increasing nickel salt to alkanethiol ratio
is consistent with nanoparticle formation. If the peak located at 2.4 eV and 2.1 eV were
assigned to the band gap energy of C6-NiS (rt, 2x, 0.1x) and C6-NiS (rt, 3x, 0.1x),
respectively, the particle size would be smaller for increasing nickel salt to alkanethiol
117
ratios. A decrease in band gap energy for increasing nickel salt to alkanethiol ratios is
not consistent with other studies of semiconductor nanoparticles.44 The excess
alkanethiols should create a smaller nanoparticles size, because in the formation of NiS
cores, S2- displaced the alkanethiolate ligands in the RS-Ni polymers and clustered the
neighboring nickel ions forming the nanosized structure; hence, the more alkanethiols
present, the less likely they will be replaced by S2-. The inability to displace alkanethiols
yields the formation of smaller particle sizes as the nickel ions cant cluster together.
1.2
(rt, 2x, 0.1) 340 nm 3.65 eV

(rt, 3x, 0.1) 337 nm 3.67 eV
(rt, 2x, 0.1)

(rt, 3x, 0.1)
1.0
Absorbance
0.8
0.6
420 nm 2.96 eV
(rt, 2x, 0.1) 526 nm 2.4 eV

(rt, 3x, 0.1) 590 nm 2.1 eV
0.4
0.2
0.0
-0.2
200
300
400
500
600
700
800
900
(nm)
Figure 5.4. UV-Vis Profile of C6-NiS particles synthesized with different feed ratios of
alkanethiol. The particles were dissolved in chloroform at a concentration of 0.033

mg/mL.
5.2.1.3 Fluorescence of NiS Nanoparticles
Semiconductor nanoparticles can have luminescent properties at room

temperature, although some are weak or non-luminescent. This low luminescence can be
118
due to either indirect band gap nature of the semiconductor or a high density of internal
and/or surface trap states that quench the luminescence.6,169-171 The fluorescence shown
in Figure 5.5 is a typical spectrum of C6NiS nanoparticles, which is almost featureless
with the exception of a few spikes from the solvent. The excitation wavelengths for the
emission spectrum were chosen from corresponding peaks of the uv-vis spectra. Also,
when a excitation spectra was taken the profile remained featureless. For most of the
samples taken the same featureless spectrum was obtained, however, one sample did
some significant luminescence. The absence of fluorescence indicates that the solutions
contain nickel (II) complexes rather than the formation of nanoparticles as they would
show fluorescence and the nickel (II) complexes will not.
2000
em=340
em=420
em=578
ex=587
1500
Emission
Excitation
1750
ex=611
1250
1000
750
500
300
400
500
600
700
800
900
(nm)
chloroform. Excitation profile was collected with emission wavelength (em) set
according to the legend, whereas for the emission spectra, the excitation wavelength (em)
was set according to the legend. The solution concentration was 0.033 mg/mL.
119
The excitation and emission profiles of C6-NiS (rt, 2x, 0.4x) are shown in Figures
5.6, 5.7, and 5.8, which correspond to the three different starting excitation peaks from
the UV-Vis spectra, 338 nm, 416 nm, and 526 nm, respectively. A broad peak emerged
at 386 nm for the emission profile when the sample was first monitored with an
excitation wavelength of 338 nm, as shown in Figure 5.6. Following the collection of
this emission profile, an excitation profile was collected using an emission wavelength of
386 nm which contained one broad excitation band that is composed of two sharp peaks
at 311 nm and 351 nm. Again, an emission profile was taken for the peaks, 311 nm and
351 nm, observed in the excitation spectrum, which displayed the same emission peak,
approximately 380 nm that was observed in the first emission profile. The fluorescence
from the emission spectrum excited at 338 nm indicates that the 338 nm peak in the UVVis measurements can be assigned to the band gap energy of NiS nanoparticles. Figure
5.8 shows the emission profile for NiS (rt, 2x, 0.4x) with an excitation wavelength of 526
nm, which is featureless, therefore, the peak at ~520 nm in the UV-Vis data can not be
attributed to the band gap energy of NiS nanparticles.
120
em=338
ex=386
em=311
1.0
ex=380
em=309
em=351
em=396
em=353
Emission
Excitation
0.8
0.6
0.4
0.2
0.0
200
300
400
500
600
700
Wavelength (nm)
chloroform. The excitation profile was collected with emission wavelength (em) set
according to the legend, whereas for the emission spectra, the excitation wavelength (em)
was set according to the legend. The solution concentration was 0.033 mg/mL. The first
em was chosen as 338 nm from the corresponding UV-Vis data. These spectra were
normalized to their respective maximum intensity.
121
1.2
em=416
ex=466
Emission
Excitation
1.0
0.8
0.6
0.4
0.2
300
400
500
600
700
800
900
Wavelength (nm)
chloroform. The excitation profile was collected with emission wavelength (em) set to
466 nm, whereas for the emission spectra, the excitation wavelength (ex) was set to 416
nm. The solution concentration was 0.033 mg/mL. The first em was chosen as 416 nm
from the corresponding UV-Vis data. These spectra were normalized to their respective
maximum intensity.
122
1400
em=526
Emission
1200
1000
800
500
600
700
800
900
Wavelength (nm)
the emission spectra, the excitation wavelength (ex) was set according to the 526 nm
peak from the corresponding UV-Vis Profile. The solution concentration was 0.033
mg/mL.
The alkanethiol chain length was also varied in the synthetic protocol. The
emission profile of C5-NiS (rt, 2x, 0.5x) is given in Figure 5.9, which is featureless for all
excitation wavelengths. The corresponding UV-Vis profile has similar peaks to that
show in Figures 5.3 and 5.4 with peaks at 338, 416, and 512 nm.
In general, the photoluminescence is featureless for NiS nanoparticles, akin to
Figures 5.5 and 5.9. When the photoluminescence experiments were repeated for C6-NiS
(rt, 2x, 0.4x), a featureless profile was obtained. The origin of the luminescence could be
due to the electronic structure of the NiS nanoparticles or due to impurities. The absence
123
of luminescence in other samples of NiS and the repeated sample indicate that the
luminescence was due to something other than NiS nanoparticles.
1400
em=252
em=294
1200
em=338
Emission
em=416
em=512
1000
800
600
400
300
400
500
600
700
800
900
(nm)
the emission spectra, the excitation wavelength (ex), 252, 294, 338, 416, and 512 nm,
was chosen from the corresponding UV-Vis Profile. The solution concentration was
0.033 mg/mL.
5.2.1.4. Electrochemistry of NiS
From the UV-Vis profile, absorption features are present at energies of 4.93eV,
3.68 eV, 2.98 eV, and 2.43e V for NiS nanoparticles with an optical band gap energy of
approximately 3.68 eV. This means that for the electrochemistry a large potential
window will need to be used. An appropriate solvent and electrolyte combination for
124
these experiments with a large potential window is THF and TBAP, which results in a
working potential window from 1.0 V to -3.4 V vs. a Ag/AgCl wire.172
Figure 5.10 depcits the cyclic voltammogram (CV) of C6-NiS (rt, 3x, 0.1x) and
0.1 M TBAP dissolved in THF. Initially, the potential sweeps from 0 V in the cathodic
direction, which is then followed by a sweep in the anodic direction. The potential
window was slowly expanded in the negative and positive directions as indicated by the
legend in Figure 5.10. The CV is essentially featureless, i.e. flat, until the potential
region is expanded between -1.6 V and 1.0 V (the brown curve) where the current starts
to increase drastically at the positive potential end and the current appears to be taking
off at the negative potential end. This flat region can be attributed to the
electrochemical band gap energy, which can be approximated as 2.4 eV from the current
take off areas of -1.6 V and 0.8 V, which is different than the optical band gap
assignment. The potential window was expanded to -2.0 V in the negative direction, as
shown in Figure 5.11. Five peaks can be found in this region labeled as A, B, C, D, and
E in Figure 5.11, which are located at -1.720 V, -1.554 V, -0.856 V, -0.436, and 0.824 V,
respectively. The peak located at B is actually two peaks located around -1.554 V and 1.484 V, which will be examined more closely during differential pulse voltammetry
experiments to be discussed later. Although the detailed mechanism is unknown, it is
likely that these voltammetric features can be ascribed to the anodic decomposition of
NiS at positive potentials. The decomposition of semiconductor nanoparticles at very
positive and negative potentials has been described previously.44,160,173 Analogous to the
dissolution of PbS nanoparticles44,160, the decomposition pathways can be described as
Anodic dissolution:
NiS Ni2+ + S + 2e
125
(5.2)
Cathodic dissolution: NiS + 2H+ + 2e Ni + H2S
(5.3)
0.8
0.2 to -0.2
0.4 to -0.4
0.6 to -0.6
0.8 to -0.8
1.0 to -1.0
1.0 to -1.2
1.0 to -1.3
1.0 to -1.4
1.0 to -1.6
Current (A)
0.6
0.4
0.2
0.0
-0.2
-1.5
-1.0
-0.5
0.0
0.5
1.0
Potential (V) vs Ag/AgCl

Figure 5.10. Cyclic Voltammograms of a Au electrode (0.80mm2) in 1 mg / 1mL of C6-
NiS (rt, 3x, 0.1) and 0.1M TBAP dissolved in THF with varied potential windows. The
potential sweeps were started cathodically, and the sweep rate is 100 mV/s. The legend
depicts the potential regime for each scan.
126
1.0
E
Current (A)
0.5
D
0.0
-0.5
A
-1.0
-1.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0

NiS (rt, 3x, 0.1) and 0.1M TBAP dissolved in THF. The potential sweep was started
cathodically, and the sweep rate was 100 mV/s.
The peaks observed in the CVs of C6-NiS (rt, 3x, 0.1x) as seen in Figure 5.11
were examined more closely using differential pulse voltammetry (DPV). Figure 5.12
depicts the DPV of C6-NiS (rt, 3x, 0.1x) and 0.1M TBAP in THF. Here the
electrochemical band gap energy can be determined more precisely than from the CV
profile in Figure 5.10. The spacing between the first negative and positive voltammetric
peaks, as indicated by the arrows in Figure 5.12, corresponds to the electrochemical band
gap energy. Using these peaks, the electrochemical band gap energy is 2.412 eV, which
does not agree well with the optical band gap energy of 3.68 eV. Peaks C and D in the
CV data due in fact correspond to two irreversible peaks in the DPV profile, whereas,
peaks A, B, and E all have a clear, distinct return wave in the DPV profile.
127
The electrochemical band gap energy of C6-NiS (rt, 3x, 0.1x) was calculating in
the same manner as above using the first negative and positive peaks shown in Figure
5.13. The calculated electrochemical band gap energy is 2.47 eV, which is different than
the optical band gap energy, 3.67 eV.
0.4
0.840
-1.620
Current (A)
0.2
-1.852
-1.492
-1.388
-0.956
-0.472
0.0
-0.2
0.792
-1.796
-0.4
-1.580
-0.6
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0

1mL of C6-NiS (rt, 3x, 0.1) and 0.1M TBAP dissolved in THF.
5.2.2 Solventless Synthesis of NiS nanoparticles
In addition to synthesizing NiS nanoparticles in a solution based approach under

ambient conditions, the solventless, thermolytic decomposition of nickel thiolate
precursors was used as well. Ghezelbash and co-workers used this solventless method to
synthesis CuS and NiS nanoparticles.61,146 Although they couldnt pinpoint an exact
mechanism for NiS growth, they were able to determine relationship between reaction
128
parameters with the size and shape of nanoparticles. For instance, they determined that
increasing the reaction temperature simply increased the growth rate of nanoparticles,
which lead to much larger sizes. On the other hand they found that the reaction time had
little effect on the synthesized products. Another important factor was the overall
concentration of reaction species. In particular, increasing the concentration led to the
development of nanoprisms, whereas at lower concentrations nanorods were the
dominant product. It is important to note that the nickel/thiol/dodecanoate ratio is the
same; the concentration of all species is increased to form nanoprisms. Following the
same procedure as Ghezelbash, we were able to easily synthesize several samples of NiS
nanoparticles under different reaction conditions: reaction concentration and reaction
temperature. In particular we synthesized C12-NiS (68/95/100) at 190oC for 2 hours, C12NiS (58/80/86) at 190oC for 2 hours, and C12-NiS (58/80/86/) at 210oC for 1 hour to
monitor their optical and electrochemical properties.
5.2.2.1 Optical Measurements of NiS Nanoparticles
The UV-Vis and fluorescence spectra are shown in Figures 5.14-5.19. The UVVis spectrum for C12-NiS (58/80/86) at 190oC for 2 hours is shown in Figure 5.14, which
is a relatively featureless with the exception of a peak at 310 nm. Two other peaks were
determined from the second derivative of the UV-Vis spectrum at 384 nm and 470 nm;
however, it is quite possible that these peaks are due to noise present in the spectrum.
Nevertheless, these peaks were used as the excitation wavelengths in the
photoluminescence of this NiS sample, which is shown in Figure 5.15. The most
prominent fluorescent peak occurred at 482 nm with the corresponding excitation peak at
386 nm.
129
The UV-Vis and fluorescence spectrums are quite different for the NiS
nanoparticles synthesized at a higher ratio of reaction precursors, i.e. C12-NiS (68/95/100)
at 190oC for 2 hours as shown in Figures 5.16 and 5.17. This sample should contain
more nanoprisms versus nanorods than the previous sample shown in Figure 5.14 and
5.15. Overall, the UV-Vis spectrum in Figure 5.16 appears to be very similar to the UVVis spectrum of C12-NiS (58/80/86) at 190oC for 2 hours shown in Figure 5.14, however,
there are no obvious peaks presents. Peaks at 270 nm, 306 nm, and 410 nm were located
and used for the excitation wavelengths in the fluorescence studies. When excited at 410
nm, the NiS nanoparticles exhibit a broad emission peak at 515 nm, shown in Figure
5.17. This fluorescence peak is red-shifted in comparison to the fluorescence observed at
470 nm of C12-NiS (58/80/86) at 190oC for 2 hours and could be indicative of the
difference in electronic structure of nanorods vs. nanoprisms.146
Figure 5.18 and 5.19 show the UV-Vis and fluorescence measurements of C12NiS (58/80/86) at 210oC for 1 hour, respectively. The UV-Vis is featureless with a small
visible peak at 310 nm, which is the same peak position as C12-NiS (58/80/86) at 190oC
for 2 hours. Interestingly, the fluorescence profile is also very similar with a fluorescence
peak at 482 nm and an excitation peak at 388 nm. The NiS nanoparticle size was
expected to be much larger as the reaction temperature is increased, which would be
reflected as a red-shift in the UV-Vis and fluorescence spectra. This was not the case for
C12-NiS (58/80/86) at 210oC for 1 hour.
130
0.30
0.25
Absorbance
0.20
0.15
0.10
0.05
0.00
310
384
470
-0.05
200
300
400
500
600
700
800
900
(nm)
chloroform. The vertical lines depict the peak positions as determined by the second
derivative. The solution concentration was 0.033 mg/mL.
1.0
em=386
ex=482
Emission
Excitation
0.9
0.8
0.7
0.6
300
400
500
600
700
(nm)
nanoparticles in chloroform. The excitation profile was collected with emission
131
wavelength (em) set to 482 nm, whereas for the emission spectra, the excitation
wavelength (ex) was set to 386 nm. The solution concentration was 0.033 mg/mL. The
first em was chosen as 386 nm from the corresponding UV-Vis data. These spectra were
1.2
1.0
Absorbance
0.8
0.6
0.4
0.2
270nm
306nm
0.0
410nm
200
300
400
500
600
700
800
900
(nm)
chloroform. The vertical lines depict the peak positions as determined by the
secondrivative. The solution concentration was 0.033 mg/mL.
132
1.0
ex=515
em=410
Emission
Excitation
0.8
0.6
0.4
0.2
0.0
300
400
500
600
700
800
(nm)

wavelength (ex) was set to 410 nm. The solution concentration was 0.033 mg/mL. The
first em was chosen as 410 nm from the corresponding UV-Vis data. These spectra were
133
1.2
Absorbance
1.0
0.8
0.6
0.4
0.2
310
370
442
0.0
200
300
400
500
600
700
800
900
(nm)
Figure 5.18. UV-Vis Profile C12-NiS (58/80/86/210oC, 1hr) nanoparticles in chloroform.
The vertical lines depict the peak positions as determined by the second derivative. The
solution concentration was 0.033 mg/mL.
1.0
em=388
ex=482
em=370
em=442
ex=521
0.6
Emission
Excitation
0.8
0.4
0.2
300
400
500
600
700
800
(nm)
Figure 5.19. Excitation and Emission Spectra of C12-NiS (58/80/86/210oC, 1hr)
134
wavelength (em) set to 482 nm and 521 nm, whereas for the emission spectra, the
excitation wavelength (ex) was set to 388, 370, and 442 nm. The solution concentration
was 0.033 mg/mL. These spectra were normalized to their respective maximum
intensity.
5.2.2.2 Electrochemistry of NiS Nanoparticles
Figure 5.20 shows the CV of C12-NiS (58/80/86) heated at 190oC for 2 hrs. The
CV is relatively featureless until the potential window is expanded to -1.4 V where a
voltammetric peak occurs at approximately -1.3 V with no apparent return wave. The
potential window was expanded further to -2.0 V, but no new peaks emerged. After
cycling at different potential windows, the peak at -1.3 V decreased slightly. The DPV in
Figure 5.21 shows several small peaks in the negative region and a slightly larger peak at
0.316 V. The CV and DPV of C12-NiS (58/80/86/210oC, 1hr) is shown in Figure 5.22
and 5.23, respectively. The CV is very similar to Figure 5.20; however, no peaks are
present until the potential window is expanded to -1.8 V, which is much larger than the
CV of C12-NiS (58/80/86/190oC, 2hrs). By expanding the potential window to -1.8 V, the
cathodic current begins to increase and is accompanied by an irreversible anodic peak
located at approximately 0.078 V. When the potential window is expanded further a
cathodic peak emerges at -1.712 V with no return wave and the anodic peak current at
0.078 V increases. The peak at -1.712 V most likely arises from the cathodic reduction
of NiS nanoparticles into Ni and the corresponding alkanethiols, whereas the peak
located at 0.078V is most likely the anodic stripping of nickel accumulated on the
surface.
135
0.3
0.2 to -0.2
0.4 to -0.4
0.6 to -0.6
0.8 to -0.8
1.0 to -1.0
1.0 to -1.2
1.0 to -1.4
1.0 to -1.6
1.0 to -1.8
1.0 to -2.0
Current (A)
0.2
0.1
0.0
-0.1
-0.2
-0.3
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0

NiS (58/80/86/190oC, 2hrs) and 0.1M TBAP dissolved in THF. The potential sweep was
started cathodically, and the sweep rate was 100 mV/s.
0.4
Current (A)
0.3
0.2
0.1
0.080
-1.528
-1.080
0.0
-1.450
-0.1
-1.726
-0.2
-0.3
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0

1mL of C12-NiS (58/80/86/190oC, 2hrs) and 0.1M TBAP dissolved in THF.
136
0.8
0.2 to -0.2
0.4 to -0.4
0.6 to -0.6
0.8 to -0.8
1.0 to -1.0
1.0 to -1.2
1.0 to -1.4
1.0 to -1.8
1.0 to -2.0
Current (A)
0.6
0.4
0.2
0.0
-0.2
-0.4
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
NiS (58/80/86/210oC, 1hr) and 0.1M TBAP dissolved in THF. The potential sweep was
started cathodically, and the sweep rate was 100 mV/s.
0.3
Current (A)
0.2
0.1
-1.861
0.078
-1.450
-1.235
0.0
-1.380
-0.1
-1.712
-0.2
-0.3
-2.0
-1.5
-1.0
-0.5
0.0
137
0.5
1.0
1mL of C12-NiS (58/80/86/210oC, 1hr) and 0.1M TBAP dissolved in THF.
5.2.3 Comparison of Liquid Phase Synthesis to the Solventless Synthesis
Two different methods were used to synthesize NiS nanoparticles, a liquid

synthesis and a solventless synthesis. The products obtained using the liquid synthesis
were often oily and difficult to purify, whereas the products obtained using the
solventless route were flaky and much easier to purify and handle. The optical properties
were quite different for the two different routes. The UV-Vis profile obtained for the
products of the liquid phase synthesis had three distinct peaks at 338 nm, 420 nm, and
520 nm. However, only one sample showed fluorescence when excited at 338 nm, 3.67
eV; however, this fluorescence was not reproducible. The lack of fluorescence indicates
that nanoparticles were not formed during the synthesis, indicating the UV-Vis peaks
arose from Ni(II) complexes. In contrast, the samples produced from the solventless
route had fluorescence peaks at different excitation energies. So, NiS nanoparitlces were
synthesized and the size and/or shape could be controlled by varying the concentration of
the reaction precursors. The electrochemistry of the products from the different synthetic
routes was quite different. Peaks were present in the solventless synthesis of NiS
nanoparticles that are the obvious oxidation of Ni metal accumulated on the electrode
surface.
5.3 HgSe
5.3.1 Synthesis
138
HgSe nanoparticles were synthesized using a liquid phase method which is

discussed in more detail in Chapter 2. In the typical reaction a 1 mmol of mercury salt
was dissolved in methanol which produced a light pink solution. To this solution 2 mmol
of C6SH was added and the solution immediately turned white. After the addition of
toluene and 0.1 mmol of sodium diselenide, the solution turned a greenish brown color.
The resulting product was purified and found to be soluble in apolar solvents. This
sample was denoted as C6-HgSe (rt, 2x, 0.1x) to indicate the Hg salt: alkanethiol: sodium
diselenide ratio. The next sample synthesized was C6-HgSe (rt, 1/2x, 0.1x), which was
not soluble in polar or apolar solvents: chloroform, dichloromethane, hexanes,
tetrahydrofuran, toluene, acetonitrile, N,N-dimethylformamide, watter, methanol,
ethanol, acetone, isopropyl alcohol, or dimethyl sulfoxide. Other samples synthesized
that yielded soluble products were C6-HgSe (rt, 1x, 0.2x), C6-HgSe (rt, 4x, 0.1x), C12HgSe (rt, 1x, 0.2x), C12-HgSe (rt, 4x, 0.1x), and C12-HgSe (rt, 4x, 0.2x).
5.3.2 Optical Measurement of HgSe Nanoparticles
Figure 5.24 shows the UV-Vis profile of C6-HgSe (rt, 4x, 0.1x), which follows an
exponential decay pattern with the presence of a small peak at 368 nm. Similar to other
studies, the peak positions were located by the taking the second derivative of the UVVis profile. For this sample, other peaks were located at 440 nm, 470 nm, and 512 nm.
These peaks were then used as the excitation wavelength for fluorescence studies shown
in Figure 5.25. Each excitation resulted in the absence of fluorescence, which indicates
that HgSe nanoparticles were not produced for the synthesis of C6-HgSe (rt, 4x, 0.1x).
Figure 5.26 shows the UV-Vis profile of C12-HgSe (rt, 1x, 0.2x), which is an exponential
decay with the absence of peaks. The second derivative picked up peaks at 300, 382,
139
430, 492, 536, 590, 622, and 766 nm, which were then used as the probing wavelengths
for photoluminescence studies. The UV-Vis spectrum shown in Figure 5.26 is rather
noisy, which can explain the numerous peaks picked up on closer analysis; however,
these peaks were still used for the photoluminescence studies shown in Figure 5.27.
Again, there is an absence of emission at all wavelengths probed, indicating that this
sample, C12-HgSe (rt, 1x, 0.2x), also did not produce HgSe nanoparticles. Figure 5.28
shows the UV-Vis profile for C12-HgSe (rt, 4x, 0.1x), which shows a similar profile to
C6-HgSe (rt, 4x, 0.1x), i.e. an exponential decay with a small peak at 386nm. Other
peaks were located at 442 nm and 486 nm, but none of them produced fluorescence as
shown in Figure 5.29. Figure 5.30 shows the UV-Vis profile of C12-HgSe (rt, 4x, 0.2x),
which has an exponential decay pattern with peaks at 348 and 384 nm. Unlike the other
samples, a fluorescence peak was observed at 410 nm when the excitation wavelength
was set to 348 nm; hence, to produce HgSe nanoparticles, the reaction conditions should
be a four-fold excess of C12SH to Hg salt as well as a 0.4-fold excess of sodium
diselenide to Hg salt.
140
0.35
Absorbance
0.30
0.25
0.20
470nm
512nm
0.15
0.10
300nm
0.05
368nm
440nm
0.00
200
300
400
500
600
700
800
900
(nm)
vertical lines depict the peak positions as determined by the second derivative. The
solution concentration was 0.033 mg/mL
2600
em= 368
2400
em= 300
em= 512
Emission
2200
em= 440
em= 470
2000
1800
1600
1400
1200
300
400
500
600
(nm)
141
700
800
900
The emission spectra were collected with an excitation wavelength (ex) was set to 300,
368, 440, 470, and 512 nm. The solution concentration was 0.033 mg/mL.
0.07
0.06
Absorbance
0.05
0.04
0.03
0.02
0.01
0.00
300
382
430 492 536 590 622
766
-0.01
200
300
400
500
600
700
800
900
(nm)
solution concentration was 0.02 mg/mL
142
2000
em= 300
1800
em= 382
em= 430
Emission
1600
em= 492
1400
em= 536
1200
em= 652
1000
em= 766
em= 590
em= 622
800
600
400
200
300
400
500
600
700
800
900
1000
Wavelength (nm)
The emission spectra were collected with an excitation wavelength (ex) was set to 384
and 534 nm. The solution concentration was 0.033 mg/mL.
3.5
Absorbance
3.0
2.5
2.0
1.5
1.0
386
442 486
0.5
300
400
500
600
(nm)
143
700
800
900
6000
em=386
5000
em=442
Excitation
em=486
4000
3000
2000
1000
400
500
600
700
800
900
(nm)
The emission spectra were collected with an excitation wavelength (ex) was set to 386,
442, and 486 nm. The solution concentration was 0.02 mg/mL.
144
0.5
Absorbance
0.4
0.3
0.2
0.1
0.0
348 384
200
300
400
500
600
700
800
(nm)
2400
em = 348
em = 440
Emission
Excitation
2100
1800
1500
1200
900
200
300
400
500
(nm)
145
600
700
Figure 5.31. Excitation and Emission Spectra of C12-HgSe (rt, 4x, 0.2x) nanoparticles in
chloroform. The excitation spectrum was collected with an emission wavelength (em) of
440 nm and the excitation spectrum were collected with an excitation wavelength (ex)
was set to 348 nm. The solution concentration was 0.033 mg/mL.
5.4 Ag2S
5.4.1 Synthesis
Ag2S nanoparticles were synthesized using the solventless, thermolytic

decomposition of silver thiolate precursors, which was also used to synthesize
NiSnanoparticles. Two samples were synthesized successfully, C12-Ag2S (58/80/86)
heated at 150oC for 45 minutes and 1.5 hours.
5.4.2 Optical Measurements of Ag2S Nanoparticles
Figures 5.32 and 5.33 show the UV-Vis and fluorescence profile, respectively, for
C12-AgS (58/80/86) heated at 150oC for 45 minutes. The UV-Vis profile shows a sharp
excitonic peak at 292 nm with two smaller peaks at 360 nm and 390 nm. The
corresponding fluorescence measurements show no luminescence for any of the
excitation wavelengths. When a C12-Ag2S (58/80/86) sample is heated for an hour and
45 minutes, a slight change is apparent in the UV-Vis measurements as seen in Figure
5.34. Now the excitonic peak has slightly red-shifted and has decreased in intensity. The
corresponding luminescence is drastically different as seen in Figure 5.35, which contains
a fluorescence peak at 424 nm and an excitation peak at 346 nm. The luminescence seen
from the C12-Ag2S (58/80/86) reaction conditions indicates that Ag2S nanoparticles were
146
formed and that the sample should be heated for at least an hour and a half to form
nanoparticles.
0.20
Absorbance
0.15
0.10
0.05
0.00
292
360 390
-0.05
200
300
400
500
600
700
800
900
(nm)
Figure 5.32. UV-Vis Profile C12-Ag2S (58/80/86/150oC, 45min) nanoparticles in
chloroform. The solution concentration was 0.033 mg/mL.
147
3000
Fluorescence Intensity
em =292
ex=375
2500
em=331
em=360
em=390
2000
1500
1000
500
200
300
400
500
600
700
(nm)
Figure 5.33. Excitation and Emission Spectra of C12-Ag2S (58/80/86/190oC, 45min)

wavelength (ex) was set to 292, 331, 360, and 390 nm. The solution concentration was
0.033 mg/mL. These spectra were normalized to their respective maximum intensity.
148
0.30
0.25
Absorbance
0.20
0.15
0.10
0.05
0.00
-0.05
200
294
300
346
400
500
600
700
800
900
(nm)
Figure 5.34. UV-Vis Profile C12-Ag2S (58/80/86/150oC, 1.5hrs) nanoparticles in
chloroform. The solution concentration was 0.033 mg/mL.
1.0
em=346
ex=424
em=366
ex=434
Emission
Excitation
0.8
em=356
0.6
0.4
0.2
300
400
500
(nm)
600
700
Figure 5.35. Excitation and Emission Spectra of C12-Ag2S (58/80/86/190oC, 1.5hrs)
149
wavelength (em) set to 424 and 434 nm, whereas for the emission spectra, the excitation
wavelength (ex) was set to 346, 366, and 356 nm. The solution concentration was 0.033
mg/mL. These spectra were normalized to their respective maximum intensity
5.4.3. Electrochemical Measurements of Ag2S Nanoparticles
Figure 5.36 shows the CV of C12-Ag2S (58/80/86) heated at 150oC for 45 minutes.
In the smallest potential window an anodic peak is located at 0.5 V and decreases as more
scans are taken with larger potential windows. As the potential window is expanded to 1.2 V a cathodic peak emerges at -1.1 V. Upon further expansion of the potential
window another cathodic peak is located at -1.5 V. The DPV of C12-Ag2S (58/80/86)
heated at 150oC for 45 minutes, shown in Figure 5.37, gives a precise location of the
reduction and oxidation peaks. The fluorescence experiments of C12-Ag2S (58/80/86)
heated at 150oC for 45 minutes did not show luminescence indicating Ag2S nanoparticles
were not formed for that sample; therefore, the peaks shown in Figure 5.36 and 5.37 are
not due to Ag2S nanoparticles. In fact, the peak located at 0.5578 during the cathodic
scan can be attributed to the reduction of Ag(I) to Ag.
Figure 5.38 shows the CV of Ag2S (58/80/86) heated at 190oC for 1.5 hr. This
sample did produce Ag2S nanoparticles with an optical band gap energy of 3.67 eV,
which is a large band gap energy. The potential window was not wide enough to
determine the electrochemical band gap energy. The CV in Figure 5.38 has several peaks
that increase each time the potential window increases. The DPV for this sample is
shown in Figure 5.39 with anodic peaks at -0.4930 V, 0.0924 V, and 0.630 V. Cathodic
150
peaks are located at -1.1309, -0.5088, -0.1500, and 0.9120 V. Unlike the previous
example, these peaks cannot be attributed to the Ag(I) species.
0.4
Current (A)
0.2
0.0
-0.2
-0.4
0.8 to -0.8
1.0 to -1.0
1.0 to -1.2
1.0 to -1.4
1.0 to -1.6
1.0 to -1.8
1.0 to -2.0
-0.6
-0.8
-1.0
-1.2
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0

Ag2S (58/80/86/190oC, 45 minutes) and 0.1M TBAP dissolved in THF. The potential
sweep was started cathodically, and the sweep rate was 100 mV/s.
151
0.3
Current (A)
0.2
0.1
0.9188
-1.3818
0.5578
-0.5715
0.0
-1.068
0.5685
-0.708
-1.458
-0.1
-0.2
-0.3
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0

1mL of C12-Ag2S (58/80/86/190oC, 45 min) and 0.1M TBAP dissolved in THF
1.0
0.8 to -0.8
1.0 to -1.0
1.0 to -1.2
1.0 to -1.4
1.0 to -1.8
1.0 to -2.0
Current (A)
0.5
0.0
-0.5
-1.0
-1.5
-2.0
-2.0
-1.5
-1.0
-0.5
0.0
152
0.5
1.0
Ag2S (58/80/86/190oC, 1.5 hrs) and 0.1M TBAP dissolved in THF. The potential sweep
was started cathodically, and the sweep rate was 100 mV/s.
0.6
0.4
-0.4930
0.6320
Current (A)
0.0924
0.2
0.0
-0.2
0.1500
-1.1309
0.9120
-0.4
-0.6
-2.0
-0.5088
-1.5
-1.0
-0.5
0.0
0.5
1.0

1mL of C12-Ag2S (58/80/86/190oC, 1.5 hrs) and 0.1M TBAP dissolved in THF
5.5 Summary
Solventless and liquid phase approaches were used to synthesize NiS

nanoparticles. The liquid phase synthesis yielded products that were difficult to handle
because they were very oily. This method did not yield any reproducible fluorescence
indicating that NiS nanoparticles were not formed. Most likely the product obtained was
a Ni(II) complex with the alkanethiol. The solventless synthesis yielded products that
were easy to handle and exhibited fluorescence. By increasing the concentration the
153
fluorescence red-shifted suggesting that NiS nanoprisms have a larger band gap energy
than NiS nanorods
HgSe nanoparticles were also synthesized using a liquid phase approach, however
only one sample had fluorescence. This fluorescence occurred at a reaction condition of
C12-HgSe (rt, 4x, 0.2x). Ag2S nanoparticles were synthesized using the solventless
method and produced Ag2S nanoparticles if the sample was heated for at least 1.5 hours.
The synthesis of Ag2S and NiS nanoparticles using the solventless, thermolytic
decomposition of reaction precursors proved promising for both materials. The ratio of
reaction precursors, heating temperature, heating time, and concentration of reaction
precursors should be extended to provide a more rigorous study of this reaction method.
Also, transmission electron microscopy would couple very nicely with the optical and
electrochemical measurements of the produced nanoparticles. Because this method is
promising for Ag2S and NiS, it could also be extended for the HgSe reactions.
154
CHAPTER 6
GOLD NANOPARTICLE BASED CHEM- & SIZE- SELECTIVE
ELECTROCHEMICAL SENSOR
6.1 Background and Motivation
Advances in nanotechnology are made on two fronts: the size and shape selective
synthesis of stable, monodisperse nanoparticles and the assembly of these nanoparticle
building blocks into functional nanodevices. Among the many nanodevices that rely on
the fabrication of nanoarchitectures, the most important are chemical and biological
sensors.1,174-178 For instance, by binding a biological macromolecule to the surface of a
nanoparticle, biological binding events with conformational or charge state changes can
be monitored electrochemically.
With the advances in the synthesis of size selective, stable, and highly
monodisperse gold nanoparticles14,58,59,179,180, organization of these nanoparticles into
organized assemblies is of the uptmost importance. There are a wide variety of methods
for precisely determined nanoarchitecture development: lithographic approaches181-185,
imprint lithography186,187, self-assembly of monolayers188, and Langmuir-Blodgett (LB)
thin film assemblies163,165,189,190 to name a few. Among these techniques, the LB
technique is a well-established method for creating compact, ordered monolayers or
multilayers on the air/water interface.4,163,189-197 Recently, Chen demonstrated that twodimensional LB monolayers of Au nanoparticles using dithiol bridging linkers are stable,
long-range ordered monolayer films and have a hexagonal close packed arrangement.190
In fact the electrical properties of the Au nanoparticle assembly was found to vary from a
155
solution of Au MPCs and with nanoparticle spacing within the film.163 The LB technique
is quite versatile as the number of monolayers and the interparticle spacing in the film is
quite easy to control. The interparticle spacing can be manipulated in two ways, by
depositing the monolayer onto a substrate at different surface pressures and by
introducing a chemical bridging linker to tether the nanoparticles together where the
length and chemistry of the bridging linker can be easily changed and provides better
stability to the film. By depositing these hexagonal close packed Au MPCs on a
substrate, an array of Au MPC islands can be immobilized. Furthermore, the alkanethiol
can be exchanged to change the functionality of the capping ligand or be completely
removed photochemically by ultraviolet and ozone molecular cleaning as shown in
Figure 6.1, which leaves an array of Au nanoislands.
UVO Exposure
Figure 6.1. The removal of alkanethiol from the Au nanoparticle surface.
The choice of substrate for particle deposition is an important decision,

particularly for use in electrochemical devices. Carbon electrodes are an excellent choice
for electrochemical studies and nanosensor development as they are widely used in
industry and are very stable.198,199 Also, the surface modification of carbon fibers can be
achieved easily using different modification methods. One of the standard methods for
156
the derivatization of carbon surfaces involves vigorous oxidation processes. These

processes lead to a surface that has a carboxylic, ketonic, or hydroxylic group, which can
be further modified by attaching a molecule to these functional groups.198,199 Although
the oxidation process is a standard procedure, it is difficult to control the number and
nature of the surface species.198,199 Another versatile method for the modification of
carbon surfaces, as described by Saveant and co-workers, is the covalent attachment of
aryl radicals onto the carbon surface through the electrochemical reduction of diazonium
salts as discussed in more detail in Chapter 2.
The creation of Au nanoassemblies on a graphite electrode yields a versatile
electrochemical sensor. One can envision the many choices of Au interparticle spacing
and the chemical modification to the Au or carbon surface to provide a powerful, easily
manipulated electrode to be used in a wide variety of systems for analysis. For example,
by varying the spacing between the Au nanoparticles and blocking the Au surface to
analyte with an appropriate capping ligand, channels to the graphite surface will be
created; hence, these channels could be used as a size selective electrochemical sensor.
That is, only molecules small enough to diffuse to the graphite (electrode) surface will be
analyzed. In addition, the Au or graphite surface can be tailored to constructively and
selectively interact with an electrolyte, either by enhancing electron transfer to the
electrode or by the attraction or repulsion of an electrolyte to the electrode surface.
Furthermore, materials other than Au could be used to create the nano-array on the
electrode surface, which would provide another aspect of design control. For instance,
CdSe nanoparticles have been assembled using the LB method.200 The use of
semiconductor nanoparticles as the functional material for the array would be an
157
interesting choice as well, because semiconductor MPCs exhibit unique optical properties
which could be exploited for a photodetection incorporation into the sensor design.200
The purpose of this research is to demonstrate the fabrication of Au arrays on a
graphite electrode and to examine the effect of blocking the Au surface, the carbon
surface, or both in the presence of the reversible redox species, Fe2+/Fe3+. The graphite
electrode was modified using two different processes, which will be discussed in detail
later.
6.2 Au Nanoparticle Networking on a Graphite Surface
Two-dimensional networks of Au nanoparticles can be created using the LB

technique and deposited on a graphite electrode.163,189,190 Details of this procedure are
discussed in Chapter 2. The creation of a monolayer of Au nanoparticles can be
confirmed using a variety of techniques. The first is the exploitation of the cyclic
voltammogram (CV) of the Au modified graphite electrode in 0.1 M H2SO4 as Au has
very distinct oxidation and reduction peaks at 1.2 V and 0.65 V, respectively. The area of
these peaks have long been used to determine the working area of bulk Au electrodes and
is used to confirm and calculate the amount of Au deposited on the graphite surface.
Figure 6.2 depicts the CV of a graphite electrode with a Au nanoparticle monolayer. The
typical Au oxidation and reduction peaks are clearly present, indicating that Au is present
on the graphite surface. To determine the amount of Au present, the peak area is used to
calculate the area of Au by the equation 6.1,
AuArea(cm 2 ) =
Ah *106
420 *
(6.1)
where Ah is the peak area and is the sweep rate. The Au area calculated from the CV in
Figure 6.2 is 0.1365 cm2. In addition to confirming the presence of the Au monolayer,
158
electrochemistry experiments can also determine if the structure of the monolayer is a Au

nanoisland array, particularly after exposure to UV and ozone molecular cleaning to
remove the alkanethiol from the Au surface. Of concern is melting of the Au nanoislands
to form a thin Au film during exposure to UV and ozone molecular cleaning.
200
Current (A)
150
100
Area = 0.1365 cm2
50
-50
-100
-150
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4

Figure 6.2. Cyclic Voltammogram of a electrode with a monolayer of Au nanoparticles
after UV and ozone molecular cleaning in 0.1 M H2SO4 dissolved in water. The potential
sweep was started cathodically, and the sweep rate was 100 mV/s.
First, methyl viologen is used to self-assemble to the bare Au surface, which will
provide information about the structure of the Au array. Viologen derivatives have long
been employed to form self-assembled monolayers on various surfaces, particularly gold
surfaces when the viologen moiety contains a thiol.162,201,202 One particularly interesting
aspect of viologen derivatives is their electrochemical properties, which are characterized
as very stable, fast redox reactions. Viologens can occur in three different oxidation
159
states, a dication, a radical cation, and a diradical, these different states are related by the
equilibria in equation 6.2 and 6.3.203
-
.+
V2+ + e V
.+
(6.2)
+e V
(6.3)
The first reduction step, as shown in equation 6.2, is highly reversible. The
corresponding peak currents from these redox reactions can be used to calculate the
surface coverage of the viologen on the monolayer; hence, the surface coverage of the Au
monolayer can be calculated because the violgen moieties with a thiol group will
specifically self-assemble onto the gold surface.172,203
Figure 6.3 shows the response of
a monolayer of gold nanoparticles after being immersed in a solution of methyl viologen

(V2+) for forty hours which has two well-defined anodic & cathodic peaks collected at
various scan rates. These anodic and cathodic peaks are used to calculate the surface
coverage using the equation for voltammetry for a nernstian adsorbate layer, as shown in
equation 6.4
ip =
n2 F 2
A*
4 RT
(6.4)
Figure 6.4 shows the graph of ip verses scan rate which demonstrates a linear relationship.
A linear relationship between the peak current and the sweep rate indicates that the
reaction occurs for a monolayer adsorbed onto the surface rather than the diffusion of
species to the electrode surface. The calculated surface coverage of V2+ on the Au
mole
surface from the slope in Figure 6.4 is 1.351x10-9 cm 2 . In a previous paper, the
160
hexagonal pattern of the Au thin was altered only slightly after UV and ozone molecular
cleaning.190 The Au monolayer was collected at a trough area of 225 cm2, which
corresponds to a nanoparticle area of 21.4 nm2/Au particle. This means that there are
173.9 V2+/Au nanoparticle. Each Au nanoparticle has approximately 314 Au atoms,
which means the V2+ monolayer only covers 55.4% of the Au nanoparticles. However,
2+
-12
the surface coverage of V on a two-dimensional bulk Au electrode is 1.5210
which is equivalent to 9.151011
mole
cm 2 ,
V 2+
. If it is assumed that the Au nanoparticles melted
cm 2
to form a thin film, then the surface coverage of V2+, should be comparable to this value.
mole
Using the surface coverage of V from Figure 6.4, 1.35110 cm 2 , the corresponding
2+
viologen per area is 8.131014
-9
V 2+
, which is larger than the coverage of a twocm 2
dimensional film.
30
Current (A)
15
200mV/s
150mV/s
100mV/s
50mV/s
30mV/s
20mV/s
10mV/s
5mV/s
-15
-30
-45
-1.0
-0.8
-0.6
-0.4
-0.2
161
0.0
Figure 6.3. Cyclic Voltammogram of a graphite electrode (1.2cm2) with a deposited
monolayer of Au nanoparticles with V2+ self assembled on the Au surface. The modified
electrode was analyzed in 0.1 M NH4NO3 dissolved in water. The potential sweep was
started cathodically, and the sweep rate was varied from 5 - 200 mV/s.
40
Current (A)
30
20
y=-4.870e-3
m=0.172
r =0.998
10
0* = 1.351 * 10-9 mol/cm
0
0
50
100
150
200
250
Potential (mV) vs Ag/AgCl

Figure 6.4. Surface coverage determined from the peak current and sweep rate found in
Figure 6.3.
6.3 Blocking Effects of a Graphite/Au Nanoparticle Electrochemical Sensor
The electrochemical sensors were constructed in a manner to block the Au

surface, the graphite surface, or both to analyte. The pathway to completely block the
surface, i.e. to block both the Au nanoparticles and the graphite surface, can be done in
two different manners: block the Au surface followed by the graphite surface or to block
the graphite surface and then block the Au surface. Both of these pathways are shown in
Figures 6.5 and 6.6.
162
Graphite
Step One
Graphit e
Step Two
Graphite
Figure 6.5. Schematic illustration Method A of the modification of a graphite/Au
nanoparticle electrode. The first step entails the blocking of the graphite surface by the
electrochemical reduction of a diazonium salt, which leaves only the naked Au
nanoislands exposed to the analyte. The second step completes the blocking of the entire
surface by blocking the Au nanoisland surface by the SAM of an alkanethiol.
Graphite
Step One
Graphit e
Step Two
Graphite
Figure 6.6. Schematic illustration Method B of the modification of a graphite/Au
nanoparticle electrode. The first step entails the blocking of the Au nanoislands by the
SAM of an alkanethiol, which leaves only the graphite surface exposed to analyte. The
second step completes the blocking of the entire surface by blocking the graphite surface
through the electrochemical reduction of a diazonium salt.
6.3.1 Blocking Effects using Method A
163
For Method A and B, a monolayer of Au nanoparticles was deposited using the

LB technique, which was then exposed to short wavelength UV light to remove the
protecting alkantehiol. At this point the graphite, the gold nanoparticles, or the entire
surface could be blocked by the reduction of diazonium salts (EPD), exposure to a thiol,
or both, respectively. The terminal group and type of diazonim salt (EPD) and/or thiol
could easily be changed to radically alter the electrochemical properties of the modified
electrode. However, the purpose for this experiment is to monitor the blocking effects of
the Au, the graphite, and both surfaces.
For Method A, an unmodified graphite electrode is first analyzed in a Fe2+/Fe3+
solution as seen by the blank curve of Figure 6.7. This curve demonstrates the reversible
reduction and oxidation of the Fe2+/Fe3+ couple. Next, the graphite surface is completely
blocked with EPD and is shown as the red curve of Figure 6.7. The anodic and cathodic
currents have decreased significantly with only a small anodic and cathodic peak present,
which is likely due to an imperfect monolayer, i.e. filled with pin holes. There is an Sshape to this voltammogram, which indicates that there are tiny pin-holes in the EPD
coverage. In CV experiments, the profile of ultramicroelectrodes will be different than a
large electrode. The characteristic shape is an S-shape for ultrmicroelectrodes, which is
present in the red curve of Figure 6.7. The next step was the deposition of Au
nanoislands with the subsequent removal of organic material from the electrode surface,
which is shown as the green curve in Figure 6.7. Notice, that the peak current is almost
completely restored with only a slight increase of spacing of the peak potentials for this
completely exposed electrode. The graphite surface was then blocked leaving the Au
array exposed, which is shown in the yellow curve of Figure 6.7. Interestingly, only
164
charging current is observed with the complete absence of peaks from the Fe2+/Fe3+redox
couple. Originally, the reduction of the EPD was thought to only form a covalent bond
with the graphite surface; however, recently Au nanoparticles were synthesized by
Schiffrin204 and co-workers which are stabilized with a metal-carbon bond formed by the
reduction of a diazonium salt. Therefore, the complete blocking observed in Figure 6.7
after the reduction of EPD is most likely due blockage of the entire surface. The final
step was the immersion of the electrode in a solution with C16SH thiol, which was
originally meant to complete the blockage of the surface; however, the blue curve
demonstrates that after this immersion, widely separated peaks emerge. It is likely that
the alkanethiol was able to disrupt the monolayer of EPD, allowing Fe2+/Fe3+ access to
the electrode.
Current Density (A/cm )
150
Blank
EPD
AuC6
100
AuC6 & EPD

Au, C16SH, EPD
50
-50
-100
-150
-0.8
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8

Figure 6.7. Method A: Cyclic Voltammograms of a modified graphite electrode using
Method A. The CV was analyzed with a solution of 1mM (Ferro/Ferri)CN6 and 0.1
165
NH4NO3 dissolved in water. The potential sweep was started cathodically, and the sweep
rate was 50 mV/s.
6.3.2 Blocking Effects Using Method B
The schematic illustration of Method B is shown in Figure 6.6. After the LB

deposition and exposure to short wavelengths to remove the organic components of the
gold nanoparticles on the graphite electrode, the electrode was immersed in a solution of
a C16SH alkanethiol. Following the SAM of C16SH on the Au surface, the graphite
surface was blocked by the reduction of EPD. At each step, the electrode was analyzed
in a solution containing Fe2+/Fe3+. The black curve in Figure 6.8 depicts the exposure of
the blank graphite electrode to analyte. This curve is characterized as having two sharp
anodic and cathodic peaks with a small separation of peak potentials. The red curve
shows the CV response once the graphite electrode is completely blocked with a layer of
EPD, there is only charging current present. The green curve demonstrates the CV
response once the Au nanoparticles are deposited on the graphite surface and exposed to
UV and ozone molecular cleaning. The peak current is almost completely restored, but
the peak potential spacing is a little larger for the deposited Au nanoparticles. The next
modification step is the SAM of C16SH onto the Au surface, as shown as the yellow
curve in Figure 6.8, which demonstrates very little change from the previous curve,
which indicates that the Au surface is not blocked. For the complete blockage of the
electrode surface, the EPD is reduced on the graphite surface. The complete blockage is
demonstrated in Figure 6.8 with the blue curve. Only charging current is present,
indicating that the entire surface is blocked from the analyte.
166
Current Density (A/cm )
150
Blank
EPD
AuC6
100
AuC6 & C16SH

50
AuC6, C16SH, & EPD
-50
50mV/s
-100
-150
-0.8
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8

Figure 6.8. Method B: Cyclic Voltammograms of a modified graphite electrode using
Method B. The CV was analyzed with a solution of 1mM (Ferro/Ferri)CN6 and 0.1
NH4NO3 dissolved in water. The potential sweep was started cathodically, and the sweep
rate was 50 mV/s.
6.3.3 Comparison of Blocking Methods
In comparison of Method A and Method B, only slight differences are present.

As expected, the blank graphite response in Fe2+/Fe3+ has two reversible redox peaks for
both Methods. The coverage of the graphite surface with EPD in both Methods is
significant; however, the shape of the CV for the first Method indicates that the EPD
monolayer has some imperfections. Also, there is no difference in the response of the
thin film of gold nanoparticles for the two different methods. For instance, both have
broader peaks than the blank graphite and have the same difference in peak potential.
Because the next step was different for the two methods we cannot directly compare the
167
results, but the final curve can be compared because the graphite surface should be
completely blocked for both of the methods. Although both methods result in the surface
being blocked there is some discrepancy as to which blocks the surface more efficiently.
The complete coverage for Method B shows charging current with one tiny identifiable
oxidation peak, whereas, a small cathodic and an anodic peak are noticeable for Method
A. Surprisingly, the SAM of the alkanethiol did not block a significant amount of the Au
portion of the electrode. Also, the formation of a Au-carbon bond was not anticipated at
the time of the experiment, which led the inability to leave the Au array open to analyte
while blocking the graphite electrode.
6.4 Summary
The blocking experiments of a modified graphite electrode were discussed.

Unfortunately, the formation of a Au-carbon by the electrochemical reduction of EPD
was not expected and greatly affected the modification procedure. The blocking of the
entire surface was achieved, but the ultimate goal is to control the region of blocking to
allow nanochannels to be exposed to analyte. These blocking experiments were a first
attempt to characterize the different stages in the development of an electrochemical
sensor. The Au nano-islands were intact after exposure to short wavelength light and
could be blocked in whole or partially, by the electrochemical reduction of a diazonium
salt or the self-assembly of an alkanethiol monolayer, respectively. The self-assembly of
methyl viologen to the surface of the Au nanoparticles demonstrated the monolayer
coverage is not complete. In fact, only 50% of the Au nanoparticles were covered with
methyl viologen, which indicates that it is difficult to form a compact monolayer on the
Au nanoparticle surface using standard self-assembly of a thiol on the Au surface after
168
the exposure of Au nanoparticles to UV and ozone molecular cleaning. The graphite

surface could be easily blocked using the electrochemical reduction of a diazonium salt,
however, there was evidence that this EPD monolayer had defects or pinholes present.
For the development of a versatile electrode, new methods should be explored to

dervatize the surface of a carbon electrode. One potential method is the anodic oxidation
of carboxylates onto the carbon surface. This method generates a R radical with
subsequent attachment of the the R radical onto the carbon surface and the evolution of
CO2, according to the Kolbe reaction198,
RCO2- R + CO2 + e-
(6.5)
The R group can be easily exchanged to change the functionality of terminal group of the
monolayer on the graphite surface. It would also be interesting to explore the possibility
of incorporating the use of semiconductor nanoparticles into the deposited array,
particularly those that are capable of electrogenerated chemiluminescence. In addition to
the blocking experiments, it would be interesting to incorporate functionalities into the
manufactured monolayers that enhance the electron transfer to the electrode.
169
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180
APPENDICES
APPENDIX A
Program for Molecular Dynamic Simulations
c
c
c
c
c
c
** A MD code for computing the coalescence of transition metal clusters

** using the classical treatment.
** The last change was made on May 8 2006 by JY
--------------------------------------------------------------------
implicit real*8(a-h,o-z)
c **
dimension xx0(300,3), xx(900),eee(900),dvxx(300,3)
dimension xx1(300,3)
c **
common/para1/am,natom
common/para2/etr0,r0,rr0
common/para3/dt,nt
c **
open(unit=10,file='classical.in',status='unknown')
open(unit=20,file='classical.out',status='unknown')
open(unit=21,file='rr.out',status='unknown')
open(unit=22,file='dkin.out',status='unknown')
open(unit=23,file='molecule1.in',status='unknown')
open(unit=24,file='molecule2.in',status='unknown')
open(unit=25,file='moviecoord.out',status='unknown')
open(unit=26,file='testcoord.out',status='unknown')
c **
read(10,*)am,ak
read(10,*)etr0
read(10,*)dt,nt
c **
write(20,5)am,ak
write(20,7)etr0
write(20,6)nt,dt
c **
c ** Load in Coordinates for Molecule1
read(23,*)natom1
do i=1,natom1
read(23,*)xx0(i,1),xx0(i,2),xx0(i,3)
write(26,*)xx0(i,1),xx0(i,2),xx0(i,3)
enddo
c **
c ** Load in Coordinates for Molecule2
read(24,*)natom2
do i=1,natom2
read(24,*)xx0(i+natom1,1),xx0(i+natom1,2),xx0(i+natom1,3)
write(26,*)xx0(i+natom1,1),xx0(i+natom1,2),xx0(i+ntaom1,3)
xx0(i+natom1,1)=xx0(i+natom1,1)+11.18
write(26,*)xx0(i+natom1,1),xx0(i+natom1,2),xx0(i+natom1,3)
enddo
natom=natom1+natom2
181
c ** Set The Momentum for Molecule2

prr=dsqrt(2.0*am*etr0)
do i=natom+1,2*natom
xx0(i,1)=0.0
xx0(i,2)=0.0
xx0(i,3)=0.0
write(26,*)xx0(i,1)
write(26,*)xx0(i,2)
write(26,*)xx0(i,3)
enddo
do i=natom+natom1+1,2*natom
xx0(i,1)=-prr
write(26,*)xx0(i,1)
write(26,*)xx0(i,2)
write(26,*)xx0(i,3)
enddo
c ** Convert Two-D Variables One-D
natom=natom1+natom2
do i=1,natom
ix=(i-1)*3
ip=(natom+i-1)*3
do j=1,3
xx(ix+j)=xx0(i,j)
xx(ip+j)=xx0(i+natom,j)
enddo
enddo
c **
iwrite=1
time=0.0
write(20,*) time
write(25,14) natom
do k=1,6*natom,3
write(20,8) (xx(k+i-1),i=1,3)
enddo
do k=1,3*natom,3
write(25,15) (xx(k+i-1),i=1,3)
enddo
c **
c ** checking energy
c **
init=(natom*3)
final=(natom*6)-3
tkin10=0.0
tkin0=0.0
do i=init,final,3
tkin10=0.5*(xx(i+1)**2+xx(i+2)**2+xx(i+3)**2)/am
tkin0=tkin0+tkin10
enddo
do i=1,ntaom
do j=1,3
xx0(i,j)=xx(3*(i-1)+j)
enddo
enddo
call suttonchen(xx0,natom,pes0)
182
etotal=tkin0+pes0
write(20,10) etotal, tkin0, pes0
write(20,11) tkin10
c **
c ** checking position and momentum of COM
c **
cc for Multiple Atoms of the Same Mass
init=natom*3
final=(natom*6)-2
pcomX=0.0
pcomY=0.0
pcomZ=0.0
pcom=0.0
do i=init+1,final,3
pcomX=pcomX+xx(i)
pcomY=pcomY+xx(i+1)
pcomZ=pcomZ+xx(i+2)
enddo
pcom=dsqrt(pcomX**2+pcomY**2+pcomZ**2)
write(20,13) pcom
c **
c ** time-propagation loop starts here
c **
do nstep=1,nt
time=time+dt
call da01ad(xx,eee,6*natom,time,dt)
if (nstep.eq.(iwrite*(nt/200))) then
iwrite=iwrite+1
write(20,*) time
write(25,14) natom
do k=1,6*natom,3
write(20,8) (xx(k+i-1),i=1,3)
enddo
do k=1,3*natom,3
write(25,15) (xx(k+i-1),i=1,3)
enddo
write(21,9) time
c **
c ** Checking Energy
c **
init=natom*3
final=(natom*6)-3
tkin1=0.0
tkin=0.0
do i=init,final,3
tkin=tkin+tkin1
enddo
dtkin=tkin-tkin0
do i=1,natom
do j=1,3
xx0(i,j)=xx(3*(i-1)+j)
enddo
enddo
call suttonchen(xx0,natom,pes)
etotal=tkin+pes
183
dpes=pes-pes0
write(20,10) etotal, tkin, pes
write(22,12) time, dtkin,dpes
c **
c ** Checking Momentum of COM
c **
cc For A Large Cluster of the same mass
init=natom*3
final=(natom*6)-2
pcomX=0.0
pcomY=0.0
pcomZ=0.0
pcom=0.0
do i=init+1,final,3
pcomX=pcomX+xx(i)
pcomY=pcomY+xx(i+1)
pcomZ=pcomZ+xx(i+2)
enddo
write(20,13) pcom
endif
count=0.0
do i=1,natom
do k=i+1,natom
rx=(xx0(i,1)-xx0(k,1))**2
ry=(xx0(i,2)-xx0(k,2))**2
rz=(xx0(i,3)-xx0(k,3))**2
r=dsqrt(rx+ry+rz)
if(r.gt.50.01) then
count=count+1.0
endif
enddo
enddo
if(count.gt.1.01) then
write(20,*) time
write(25,14) natom
do k=1,6*natom,3
write(20,8) (xx(k+i-1),i=1,3)
enddo
do k=1,3*natom,3
write(25,15) (xx(k+i-1),i=1,3)
enddo
write(21,9) time, r, count
c **
c ** Checking Energy
c **
init=natom*3
final=(natom*6)-3
tkin1=0.0
tkin=0.0
do i=init,final,3
tkin=tkin+tkin1
enddo
dtkin=tkin-tkin0
do i=1,natom
184
do j=1,3
xx0(i,j)=xx(3*(i-1)+j)
enddo
enddo
call suttonchen(xx0,natom,pes)
etotal=tkin+pes
dpes=pes-pes0
write(20,10) etotal, tkin, pes
write(22,12) time,dtkin,dpes
c **
c ** Checking Position and Momentum of COM
c **
cc For Large Cluster of the Same Mass
init=natom*3
final=(natom*6)-2
pcomX=0.0
pcomY=0.0
pcomZ=0.0
pcom=0.0
do i=init+1,final,3
pcomX=pcomX+xx(i)
pcomY=pcomY+xx(i+1)
pcomZ=pcomZ+xx(i+2)
enddo
write(20,13) pcom
stop
endif
enddo
c **
c **
1 format('A+BC -> AB+C collinear Reaction Output'/)
5 format('natom=, Mass=, ForceConstant=',i5,3x,5f11.4//)
6 format('NT=',i9,2x,'DT=',f7.3)
7 format('Etr0=',f6.4,'eV',1x,'r0=',f7.3,1x,'rr0=',f6.3)
8 format('xx(i)', 3f14.7)
9 format('time,r,R,r2', 4f14.7)
10 format('etotal,t,v=',3x,f14.7,3x,f14.7,3x,f14.7)
11 format('tkin1,tkin2,tkin3=',3x,f14.7,3x,f14.7,3x,f14.7)
12 format('t,dT1,2,3,dT,dV=',3x,f14.2,3x,5f14.7)
13 format('pcom=',3x,f14.7)
14 format('Ag ',i1)
15 format('Ag',3f14.7)
stop
end
c
c -------------------------------------------------------------------c
SUBROUTINE da01ad(Y,E,N,X,H)
IMPLICIT REAL*8(A-H,O-Z)
DIMENSION Y(900),E(900),W1(900),W2(900),W3(900),W4(900)
DIMENSION F(900),F1(900),F2(900),F3(900),F4(900)
H2=H*0.5E0
X0=X
H3=H/3.0E0
185
H6=H/6.0E0
H8=H/8.0E0
CALL DYBDX(Y,F,N,X)
DO 1 I=1,N
1 W1(I)=Y(I)+H3*F(I)
X=X0+H3
CALL DYBDX(W1,F1,N,X)
DO 2 I=1,N
2 W2(I)=Y(I)+H6*(F(I)+F1(I))
X=X0+H2
DO 3 I=1,N
3 W3(I)=Y(I)+H8*(F(I)+3.*F2(I))
DO 4 I=1,N
4 W4(I)=Y(I)+H2*(F(I)-3.*F2(I)+4.*F3(I))
X=X0+H
DO 5 I=1,N
Y(I)=Y(I)+H6*(F(I)+4.*F3(I)+F4(I))
5 E(I)=Y(I)-W4(I)
c write(20,21) h8, y(1),y(2)
21 format(1x,'da01ad out=', 3f9.4)
X=X0
c
stop
RETURN
END
c -------------------------------------------------------------------SUBROUTINE dybdx(xy,DERY,N,tx)
IMPLICIT REAL*8(A-H,O-Z)
DIMENSION xy(900),DERY(900),xx(300,3),dvdri(900), dvxx(300,3)
DIMENSION veffc(9),effc(9)
common/para1/am,natom
ndery=3*natom
do i=1,ndery
dery(i)=0.098226909*xy(i+ndery)/am
enddo
do i=1,natom
do j=1,3
xx(i,j)=xy(3*(i-1)+j)
enddo
enddo
call suttonchen3(xx,natom,dvxx)
do i=1,natom
ip=(natom+i-1)*3
do j=1,3
dvdri(ip+j)=dvxx(i,j)
enddo
enddo
do i=ndery+1,n
dery(i)=-0.098226909*dvdri(i)
enddo
c write(20,20) dery(1),dery(2)
c write(20,20) (effc(i),i=1,9)
10 FORMAT(1X,'dybdx time x=',9D10.3)
186
20 format(1x,' dybdx out=', 9d10.3)

RETURN
END
c ------------------------------------------------------------------SUBROUTINE suttonchen(xx,n,v)
dimension xx(300,3)
data nv,mv,epsilon,c,a/12,6,0.0018828,144.36,4.04/
v=0.0
va=0.0
do i=1, n-1
do j=i+1, n
r2=0.0
do k=1,3
r2=r2+(xx(i,k)-xx(j,k))**2
enddo
r=dsqrt(r2)
va=va+1.0/r**nv
enddo
enddo
vb=0.0
do i=1,n
vb1 = 0.0
do j=1,n
if(j.eq.i) goto 100
r2=0.0
do k=1,3
r2=r2+(xx(i,k)-xx(j,k))**2
enddo
r=dsqrt(r2)
vb1=vb1+1.0/r**mv
100 enddo
vb=vb+dsqrt(vb1)
enddo
v = epsilon*(a**nv*va-c*dsqrt(a**mv)*vb)
return
end
c --------------------------------------------------------------------SUBROUTINE suttonchen1(xx,np,nx,n,dv)
dimension xx(300,3), dv(300,3)
c data n/4/
data nv,mv,epsilon,c,a/12,6,0.0018828,144.36,4.04/
va=0.0
!assign va
va1=0.0
!assign va1
delta=0.0
!assign delta
dv(np,nx)=0.0
!assign dv
do i=1,n
!the outer summation, up to n atoms
if(i.eq.np) then !to avoid double counting
va1=0.0
do j=1,n !inner summation, up to n atoms, but i not eq to j
if(j.eq.i) goto 200
r2=0.0
r=0.0
delta=0.0
do k=1,3
187
r2=r2+(xx(i,k)-xx(j,k))**2
enddo
delta=(xx(i,nx)-xx(j,nx))
r=dsqrt(r2)
va=(a**nv)/r**nv
va1=va1+(delta*va)/r**2
200 enddo
end if
enddo
vb=0.0
vb3=0.0
vb1 =0.0
vb2=0.0
do i=1,n
vb1=0.0
vb2=0.0
do j=1,n
if(j.eq.i) goto 400
r2=0.0
r=0.0
do k=1,3
r2=r2+(xx(i,k)-xx(j,k))**2
enddo
delta=(xx(i,nx)-xx(j,nx))
if((j.ne.np).and.(i.ne.np)) delta=0.0
if((i.ne.np).and.(j.eq.np)) delta=-delta
r=dsqrt(r2)
vb1=vb1+(delta/r**(mv+2))
vb2=vb2+(a**mv)/r**(mv)
400 enddo
vb3=1.0/dsqrt(vb2)
vb=vb+vb3*vb1
enddo
dv(np,nx) = epsilon*(-nv*va1+((a**mv)*c*mv*vb)/2)
return
end
c --------------------------------------------------------------------SUBROUTINE suttonchen3(xx,n,dv)
dimension xx(300, 3), dv(300,3)
do np=1,n
do nx=1,3
call suttonchen1(xx,np,nx,n,dv)
enddo
enddo
return
end
APPENDIX B
188
189
VITA
Graduate School
Southern Illinois University
Jennifer Yukna
Date of Birth: December 12, 1978
4055 Otter Road, Trenton, Illinois 62293

Bachelor of Science, Chemistry, May 2001
Dissertation Title:
Computational and Experimental Investigations of the Structural Properties,
Electronic Properties, and Applications of Ag, Au, HgSe, Ag2S, and NiS Nanoparticles
Major Professor: Dr. Lichang Wang
Co-Advisor: Dr. Shaowei Chen
Publications:
Yukna, J.; Wang, L. "The coalescence of Ag clusters" In Press in J. Phys. Chem.

C.
Pawluk, T.; Xiao, L.; Yukna, J.; Wang, L. "The Impact of PES on MD Results of
the Coalescence of M2 + M with M= Ir, Pt, Au, Ag" J. Chem. Theory Comput.
2007, 3, 328-335
Chen, S.; Sommers (Yukna), J.M. Alkanethiolate-Protected Copper

Nanoparticles: Spectroscopy, Electrochemistry, and Solid State Morphological
Evolution. J. Phys. Chem. B. 2001, 105, 8816-8820.
Chen. S.; Truax, L.A.; Sommers (Yukna), J.M. Alkanethiolate-Protected PbS

Nanoclusters: Synthesis, Spectroscopic, and Electrochemical Studies. Chem.
Mater. 2000, 12, 3864-3870.
190

Computational and Experimental Investigations of The Structural Computational and Experimental Investigations of The Structural Selenide, Silver Sulfide, and Nickel Sulfide Nanoparticles

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Computational and Experimental Investigations of The Structural Computational and Experimental Investigations of The Structural Selenide, Silver Sulfide, and Nickel Sulfide Nanoparticles

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COMPUTATIONAL AND EXPERIMENTAL INVESTIGATIONS OF THE STRUCTURAL

PROPERTIES, ELECTRONIC PROPERTIES, AND APPLICATIONS OF SILVER, GOLD, MERCURY

Department of Chemistry and Biochemistry

UMI Number: 3278121

UMI Microform 3278121

ProQuest Information and Learning Company

Copyright by Jennifer Yukna, 2007

AN ABSTRACT OF THE DISSERTATION OF

2.1.1.1 VASP ............................................................................................15

2.2.1.4 HgSe Nanoparticles .....................................................................33

4.3 Coalescence of Silver Clusters..........................................................................76

5.3.2 Optical Measurements of HgSe Nanoparticles ......................................139

Equation 1.1. Schrdinger Equation .............................................................................3

Equation 1.21. Basis Set ...............................................................................................11

Equation 6.2. Reduction of the viologen dication.....................................................160

Reduction of the viologen diradical cation........................................160

Surface Coverage Calculation ...........................................................160

Kolbe Reaction ..................................................................................169

constant () determined from the second derivative (dashed line) of the

denotes an initial orientation with the two

denotes an initial orientation with the two

clusters parallel to one another ...............................................................9.4

Figure 4.10. Snapshots of cluster formation at t = 40 ps from the cluster-cluster collision

denotes an initial orientation with the two

clusters parallel to one another ................................................................97

Figure 5.16. UV-Vis Profile C12-NiS (68/95/100/190oC, 2hrs) nanoparticles in

Due to the aforementioned reasons, the electronic, magnetic, optical, and

Theoretical Methods for Cluster Studies

Although the Born-Oppenheimer Approximation simplifies the full Schrdinger

determine and we can rewrite 1.8 as

As stated by Hohenberg and Kohn20 in their paper, If F [ n0 ] were a known and

By separating Ts [ n0 ] and introducing the exchange and correlation energy in 1.16,

Synthesis of Metal and Semiconductor Nanoparticles

Semiconductor and metal nanoparticles can be synthesized using a variety of

Experimental Methods for Nanoparticle Characterization

One of the most important properties of semiconductor nanoparticles is the

At room temperature, semiconductor nanoparticles have been shown to have

The electron-transfer chemistry is another interesting property of semiconductor

Design of this Dissertation

Density-Functional Theory Calculations

The Kohn-Sham Density Functional Theory Calculations were performed in the

The binding energy per atom is given by,

The magnetic moment () is calculated by

HOMO-LUMO Energy Gap

Molecular Dynamic (MD) Simulations

Classical molecular dynamic simulations use Newtons equation of motion for

and momentum, pxi , p yi , and pzi ,

The coalescence of silver clusters was investigated in two different manners:

arrow indicates the direction of the initial momentum of atom C.

2.1.2.2 Potential Energy Surface

where the pair potential is given by,

and the local electron density is given by,

given by, E = K + V, where the kinetic energy is given by K =

2.1.2.5 Calculated Quantities

Experimental Methods for Nanoparticle Synthesis and Characterization

2.2.1 Synthesis of Metallic and Semiconductor Nanoparticles

The synthesis of ethylbenzenediazonium fluoborate, C6H5N2BF4, was described

1-Hexanethiolate-protected gold (C6Au) nanoparticles were synthesized by the

tetrachloroaurate (1 mmole of AuCl4- in 20 mL of H2O) with tetra-n-octylammonium

mAuCl4-(toluene) + nC6H13SH(toluene) + 3me-

The synthesis of Au nanoparticles is summarized in equations 2.13 and 2.14. To

Larsen and co-workers demonstrated that size- and shape-monodisperse CuS

of AgNO3 (58 mmoles) to Na+-OOC(CH2)10CH3 (80 mmoles), and C12H25SH (86