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MOLECULAR DYNAMICS
A Dissertation
Doctor of Philosophy
by
Zachary L. Terranova
Abstract
by
Zachary L. Terranova
Experimental studies of solvation dynamics in imidazolium-based ionic liquids
(ILs) have revealed complex kinetics over a broad range of time scales from femtoseconds to tens of nanoseconds. Microsecond-length molecular dynamics (MD)
simulations of coumarin 153 (C153) in a series of imidazolium-based ILs were performed to reveal the molecular-level mechanism for solvation dynamics over the full
range of time scales accessed in the experiments. An analysis of the structure of the
IL in the vicinity of the probe molecule revealed preferential solvation by the cations.
Despite this observation, decomposition of the solvation response into components
from the anions and cations and also from translational and rotational motions show
that translations of the anions are the dominant contributor to solvation dynamics.
The kinetics for the translation of the anions into and out of the first solvation shell
of the dye were found to mimic the kinetic profile of the solvation dynamics response.
This mechanism for solvation dynamics contrasts dramatically with conventional polar liquids in which solvent rotations are generally responsible for the response.
The structure and dynamics of water as measured experimentally in ILs have
revealed local ion rearrangements that occur an order of magnitude faster than complete randomization of the liquid structure. Simulations of an isolated water molecule
embedded in 1-butyl-3-methyl imidazolium hexafluorophosphate, [bmim][PF6 ], were
Zachary L. Terranova
performed to shed insight into the nature of these coupled water-ion dynamics. The
theoretical calculations of the spectral diffusion dynamics and the infrared absorption
spectra of the OD stretch of isolated HOD in [bmim][PF6 ] agree well with experiment.
The infrared (IR) absorption lineshape of the OD stretch is narrow and blue-shifted
in the IL compared to the OD stretch of HOD in H2 O. Decomposition of the OD
frequency time correlation function revealed the translation of the anions dominate
the spectral diffusion dynamics.
DEDICATION
ii
CONTENTS
FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
TABLES
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
xi
ACKNOWLEDGEMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
xii
CHAPTER 1: INTRODUCTION . . . . . . . . . . . . . .
1.1 Ionic Liquids . . . . . . . . . . . . . . . . . . . .
1.1.1 Polarity of ILs . . . . . . . . . . . . . . . .
1.2 Solvation Dynamics . . . . . . . . . . . . . . . . .
1.2.1 Solvation Dynamics in ILs . . . . . . . . .
1.3 Vibrational Spectroscopy . . . . . . . . . . . . . .
1.3.1 Spectroscopic Studies in ILs . . . . . . . .
1.3.1.1 Spectroscopic Characterization of
1.3.1.2 Vibrational Reporters in ILs . . .
1
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11
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IN A SE. . . . . .
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16
16
17
17
18
19
19
21
32
35
35
39
39
39
42
57
57
60
62
CHAPTER 4: REGARDING THE VALIDITY OF LINEAR RESPONSE THEORY IN SOLVATION DYNAMICS SIMULATIONS OF IONIC LIQUIDS
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2 Computational Methods . . . . . . . . . . . . . . . . . . . . . . . . .
4.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . .
63
63
65
66
CHAPTER 5: A MOLECULAR DYNAMICS INVESTIGATION OF THE VIBRATIONAL SPECTROSCOPY OF ISOLATED WATER IN AN IONIC
LIQUID . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2 Theoretical Methodology . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.1 Spectroscopic Maps . . . . . . . . . . . . . . . . . . . . . . . .
5.2.2 Infrared Absorption Spectrum . . . . . . . . . . . . . . . . . .
5.2.3 Spectral Diffusion and Decomposition of the FFCF . . . . . .
5.2.4 Molecular Dynamics Simulations . . . . . . . . . . . . . . . .
5.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.1 IR Absorption . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.2 Spectral Diffusion . . . . . . . . . . . . . . . . . . . . . . . . .
5.4 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . .
75
75
78
78
80
81
83
85
85
92
97
3.5
iv
FIGURES
1.1
1.2
1.3
2.1
2.2
2.3
2.4
2.5
The structure coumarin 153 (C153) with the differences in charge density, q, predicted upon excitation as calculated and validated by
Cinacchi et al.[1] . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10
23
Fits of the calculated (black) and experimental (green) solvation responses of C153 in the IL [emim][BF4] to a stretched exponential function, A exp((t/ ) ), in the time range between 10 ps and 1 ns. The
data are shown as filled circles, while the fits are lines. The quality of
the fits in terms of the correlation coefficient, r2 , are excellent: r2 =
0.9987 for the theoretical data and r2 = 0.9983 for the experimental
data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
24
The calculated total simulated solvation response (black) is decomposed using the methodology described in Section 2.2.2 into contributions from the anions (red), the cations (blue), and the internal
motions of the C153 solute (purple). . . . . . . . . . . . . . . . . . .
25
28
30
2.6
2.7
31
33
3.1
Optimized structures of imidazolium cations and inorganic anions studied in this chapter. The cations are 1-butyl-3-methyl imidazolium,
[bmim], 1-ethyl-3-methyl imidazolium, [emim], while the anions are
tetrafluoroborate, [BF4 ], dicyanamide, [DCA], trifluoromethanesulfonate,
[TfO], hexafluorophosphate, [PF6 ]. . . . . . . . . . . . . . . . . . . . 36
3.2
3.3
Time constants for experiment and calculated response functions derived from a fit to a single exponential, A exp((t/ )), in the range
from 50 ps to 400 ps. . . . . . . . . . . . . . . . . . . . . . . . . . . .
44
46
47
48
49
The radial distribution function, g(r), for C153-[cation] and C153[anion] pairs, where r is defined as the distance between the center-ofmass positions of the relevant pair of molecules. . . . . . . . . . . . .
50
3.4
3.5
3.6
3.7
3.8
3.9
3.10 The solvation responses of [bmim] (blue) and [DCA] (red) decomposed
into contributions from translational (solid) and rovibrational (dashed)
motions. For reference, the total solvation response is also shown (black). 53
vi
3.11 The solvation responses of [bmim] (blue) and [PF6 ] (red) decomposed
into contributions from translational (solid) and rovibrational (dashed)
motions. For reference, the total solvation response is also shown (black). 54
3.12 The solvation responses of [emim] (blue) and [TfO] (red) decomposed
into contributions from translational (solid) and rovibrational (dashed)
motions. For reference, the total solvation response is also shown (black). 55
3.13 The residence-time correlation function (RTCF) for the anions and
cations in the first solvation shell of the C153 solute. The first solvation
shell was defined as any molecule whose center-of-mass lies within the
first solvation shell, defined as the first minimum of the cation-C153
g(r). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
56
3.14 Calculated self-diffusion coefficients for [emim] (blue) and [BF4 ] (red)
for varied unit charges. Experimental measurements (dashed) selfdiffusion coefficients for this IL in the range of 298-303 K are reported
to vary from 4.4 5.4 1011 m2 /s for [emim] and 3.6 4.2 1011
m2 /s for [BF4 ].[4] . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
58
61
4.1
4.2
4.3
4.4
5.1
68
A comparison of two decomposition strategies as applied to C0 (t) showing auto- and cross-correlation decomposition (top), to the alternative
method defined in Eq. 4.4 that calculates the contribution of the relevant component relative to the total response. . . . . . . . . . . . . .
70
71
72
86
vii
5.2
87
5.3
5.4
91
95
96
6.1
99
6.2
6.3
6.4
7.1
5.5
5.6
viii
7.2
7.3
The optimized structures of cations and anions. The cations are 1butyl-3-methyl imidazolium, [bmim], 1-ethyl-3-methyl imidazolium,
[emim], triethyl sulfonium, [S222 ], and tri(methoxymethyl)-methyl phosphonium, and [Tmet]. The anions are tetrafluoroborate, [BF4 ], trifluoromethane sulfonate, [TfO], 1-pyrazolide, [Pyrazo], 1,2,3,-triazolium, [Triazo], and bistrifluoromethylsulfonylimide, [Tf2 N] . . . . . . . . . . . . 116
7.4
7.5
7.6
7.7
7.8
7.9
ix
A.3 Fits of the calculated (black) and experimental (red) solvation responses of C153 in the IL [emim][BF4] to a single exponential function
in the time range between 50 ps and 400 ns. The data are shown as
filled circles, while the fits are lines. . . . . . . . . . . . . . . . . . . . 127
A.4 Fits of the calculated (black) and experimental (red) solvation responses of C153 in the IL [emim][BF4] to a single exponential function
in the time range between 50 ps and 400 ns. The data are shown as
filled circles, while the fits are lines. . . . . . . . . . . . . . . . . . . . 128
A.5 Fits of the calculated (black) and experimental (red) solvation responses of C153 in the IL [emim][BF4] to a single exponential function
in the time range between 50 ps and 400 ns. The data are shown as
filled circles, while the fits are lines. . . . . . . . . . . . . . . . . . . . 129
B.1 Chemical exchange 2D IR spectra for waiting times of 0 ps. . . . . . . 132
B.2 Chemical exchange 2D IR spectra for waiting times of 10 ps. . . . . . 133
B.3 Chemical exchange 2D IR spectra for waiting times of 20 ps. . . . . . 134
B.4 Chemical exchange 2D IR spectra for waiting times of 30 ps. . . . . . 135
B.5 Chemical exchange 2D IR spectra for waiting times of 40 ps. . . . . . 136
B.6 Chemical exchange 2D IR spectra for waiting times of 50 ps. . . . . . 137
B.7 Chemical exchange 2D IR spectra for waiting times of 60 ps. . . . . . 138
B.8 Chemical exchange 2D IR spectra for waiting times of 70 ps. . . . . . 139
B.9 Chemical exchange 2D IR spectra for waiting times of 80 ps. . . . . . 140
B.10 Chemical exchange 2D IR spectra for waiting times of 90 ps. . . . . . 141
B.11 Chemical exchange 2D IR spectra for waiting times of 100 ps. . . . . 142
B.12 Chemical exchange 2D IR spectra for waiting times of 200 ps. . . . . 143
B.13 Chemical exchange 2D IR spectra for waiting times of 500 ps. . . . . 144
TABLES
2.1
26
3.1
41
5.1
IR ABSORPTION DATA . . . . . . . . . . . . . . . . . . . . . . . .
88
xi
ACKNOWLEDGEMENT
xii
xiii
achieve my best. I could not have risen to the level I am now without them.
xiv
CHAPTER 1
INTRODUCTION
Ionic liquids (ILs) are gaining considerable attention because of their attractive
properties as environmentally friendly alternatives to volatile organic solvents[5, 6]
and their applications involving the production, storage, and efficient utilization
of energy[7] while also demonstrating tremendous promise in a variety of liquid
separation and extraction strategies.[8] ILs exhibit unique physical properties relative to conventional liquids in terms of vapor pressure, viscosity, electrical and
thermal conductivity, solubility of polar and nonpolar molecules, and low melting
point.[9] Moreover, these properties can be tuned to specific applications by chemically modifying the molecules that comprise the liquid, and/or by forming multicomponent mixtures of anions and cations, making ILs highly adaptable for a
variety of tasks. The use of ILs has made significant advances in electrochemical
applications[7, 10, 11], the processing of lignocellulose[1215], and thermally stable
high performance lubricants[16, 17], the practical aspects of complete control of these
reactions lies in fostering an understanding of the complex dynamics of these liquids.
In general, dynamics play an important role in determining mass and heat transport properties of reactions, which are crucial to many energy related applications.
Many proposed and actual applications of ILs involve charge-transfer reactions (e.g.
dye-sensitized solar cells, batteries, and many catalytic reactions), so understanding the detailed microscopic mechanisms and time scales of solvation dynamics in
ILs is of pressing relevance. While the solvation response has been measured in a
range of ILs, the exact molecular mechanism responsible for their complex kinetic
1
profiles has not been determined until now. This dissertation sets out to develop
a fundamental understanding of the complex intermolecular interactions in ILs that
are responsible for microscopic structures and dynamics that ultimately manifest in
macroscopic physical properties by using molecular dynamics (MD) simulations to
calculate theoretical quantities directly comparable to experimental measurements of
solvation dynamics and infrared (IR) spectroscopy.
This dissertation is organized such that a brief overview of ILs and background
material concerning solvation dynamics and IR spectroscopy are presented in the
first chapter. The second chapter focuses on calculating solvation dynamics in a
common IL, [emim][BF4 ], thus allowing a direct comparison with our experimental
collaborators. Chapter 3 then expands the solvation dynamics study over a series
of imidazolium-based ILs in addition to analyzing the effects of charge scaling on IL
properties. In Chapter 4 the validity of linear response theory as applied to solvation dynamics simulations in ILs over the entire response time is explored. The fifth
chapter describes the spectroscopic signatures of an isolated water molecule in an IL,
which acts as a probe of structure and dynamics within ILs, in addition to shedding
insight into water-ion interactions. Deviating from ILs, Chapter 6 presents calculations of multidimensional infrared spectroscopy of a non-perturbative vibrational
reporter to monitor the kinetics of proton transfer processes in aqueous solution. Finally, Chapter 7 contains concluding remarks and a summary of this work, as well as
proposed alternative systems of interest.
electrostatic interactions and frustrated packing that inhibits crystal formation. ILs
possess the advantages offered by aqueous solutions (i.e. nonflammable, high solubility of a range of compounds, efficient conductivity, etc.) and avoid certain limitations
by having a large potential window, excellent thermal stability, and the control of a
range of physicochemical properties.
Traditional molten salts were used in electrodeposition processes[18, 19] but with
operable temperatures of 1000 C, practical solution-phase applications are impossible. First generation ILs were synthesized with the goal of developing lower
temperature molten salts based on eutectic mixtures of chloroaluminates. These ILs
were able to operate at a lower temperature, however their extremely hygroscopic
nature resulted in an overproduction of HCl which limited their applicability. The
second generation ILs use ammonium, phosphonium, and most commonly imidazolium cations paired with discrete anions which offer more air and water stable
operable conditions[20] and ushered in a new era of intense IL research.
The cations examined in this dissertation, 1-butyl-3-methyl imidazolium, [bmim],
1-ethyl-3-methyl imidazolium, [emim], offer certain complexities that separate them
from inorganic cations K+ and Na+ (Figure 1.1). Their larger size and thus increased
charge delocalization decreases the lattice energy allowing these compounds to remain
liquid below 100 C. While studies examining the dependence of certain properties
on the alkyl-chain length have found changes in the viscosity[21, 22], solubility of
gases[23], and structural heterogeneity,[24, 25] the choice of the anion offers greater
control over the physicochemical properties. The favored IL 1-ethyl-3-methyl imidazolium tetrafluoroborate [emim][BF4 ] was first introduced in 1992[26] followed by
the addition of another highly fluorinated anion, hexafluorophosphate [emim][PF6 ]
in 1994[27]. Unfortunately the melting point 58-60 C made [emim][PF6 ] cumbersome until the introduction of [bmim][PF6 ] and [bmim][BF4 ] the following year.[28]
These cation anion pairs dominated the IL literature for a decade, however concerns
Cations
Anions
[bmim]
[BF4]
[PF6]
[emim]
[DCA]
[TfO]
over their aptitude to form HF gas[29] prompted the appearance of alternative anions. Trifluoromethanesulfonate, [TfO], anions emerged as interesting ILs given their
relatively lower viscosities and stability.[30] The only non-fluorinated anion surveyed
in this dissertation, dicyanamide [DCA], relies on the highly electronegative carbonnitrogen triple bond to delocalize the charge resulting in some unique properties.
Presenting some of the lowest viscosities and highest conductivities for all ILs[31],
DCA based ILs are often considered in solar cell applications.[32, 33]
(30)
scale. Representative ET
values range
from 63.1 kcal/mol for water and 30.7 kcal/mol for tetramethylsilane, the least polar
compound. Despite large variations in the different structural motifs that comprise
(30)
kcal/mol.[3436] This suggests ILs are more polar than acetonitrile (ET
(30)
of 45.6
of 49.1 kcal/mol).[34]
S(t) =
v(t) v()
v(0) v()
(1.1)
where v() is the emission frequency after the environment has completely responded
Figure 1.2. The structure coumarin 153 (C153) with the differences in
charge density, q, predicted upon excitation as calculated and validated
by Cinacchi et al.[1]
optical excitation of the probe molecule.[3436, 52, 6572] TCSPC has a time resolution of approximately 20 ps, therefore any solvation dynamics occurring faster than
20 ps are left largely unresolved. Since the TDSS often persists to 10 ns in ILs,
TCSPC is an ideal technique to capture these relatively long time scales. In practice,
though, TCSPC will miss about half of the total solvation response.[71] Several investigators have utilized fluorescence upconversion spectroscopy with sub-100 fs time
resolution[73, 74] to measure faster portions of the TDSS in ILs.[7579] By combining
the two measurement techniques, the full solvation response from 10 fs to 10 ns
is elucidated.[75, 76, 78, 79] Recently, Maroncelli, Ernsting, and coworkers have measured the TDSS of coumarin 153 (C153) in a series of ILs from 50 fs to 20 ns.[2, 3]
Immediately apparent in their results is a complex, highly nonexponential kinetic
profile with a noticeable plateau in the region between 1 and 10 ps, where the TDSS
slows appreciably. Trends with respect to varying the identity of the cations and
anions are not immediately apparent, although the slowest time scales do correlate
with viscosity (Figure 1.3).[2, 65, 69, 80]
There have been numerous experimental measurements [2, 3, 3436, 52, 6572, 75
80] in addition to a number of theoretical and simulation studies[8193] of solvation
dynamics in ILs. Kim and coworkers have examined important aspects IL dynamics,
including solvation dynamics, with both united and all-atom fully-flexible models.[84
86, 91] For the united atom studies, solvation responses were computed to time scales
as long as 1 ns, whereas shorter time scales of 10 ps were considered for the all-atom
simulations. In these studies, the solute was modeled either as a diatomic or with
a benzene-like structure. Kobrak and coworkers performed simulations of solvation
dynamics that closely mimic experiment in so much as the all-atom, fully-flexible
liquids contain a realistically modeled C153 solute.[87, 88] The solvation response
was computed to 10 ps, and a number of decomposition strategies were employed to
understand the factors responsible for the onset of solvation dynamics in ILs. In par-
10
ticular, Kobrak emphasizes the importance of the translations of the ions to the early
solvation response.[88] This is in stark contrast to conventional polar liquids, whose
short-time solvation dynamics are dominated by rotations.[41] Kobrak encountered
some difficulties in applying certain decomposition strategies to his calculated solvation response functions because of the non-pairwise additive nature of the Ewald
summation technique.[9496] Roy and Maroncelli performed extensive equilibrium
and nonequilibrium simulations of a variety of model solutes, as well as a fully atomistic C153 probe, in a coarse grained IL model.[82] For the C153 solute the computed
solvation response was in generally good agreement with experiment with the amplitude of the short time response being slightly overestimated. Roy and Maroncelli
also noted the importance of translational motions of the IL molecules to the inertial solvation response, as well as reasonable agreement between the equilibrium
and nonequilibrium solvation response functions implying the validity of the linear
response approximation. Most recently, Schmollngruber, Schrder, and Steinhauser
investigated with the solvation dynamics of C153 in three imidazolium-based ILs.[81]
Their simulations utilized an electronically polarizable force field, and their results
for the solvation response functions agree well with experiment, although the long
time decay was slightly too slow. Once again, translational motions of the molecules
were implicated as being particularly important to the solvation response. By decomposing the total response in terms of auto- and cross-correlation functions for the
anions and cations, Schmollngruber, Schrder, and Steinhauser found that the anion
and cation auto-correlation functions were similar, and the cross-correlation functions
were highly anti-correlated.
phase systems. Vibrational frequencies are susceptible to subtle changes in the surrounding electric field, shifting in frequency relative to the magnitude and direction
of the oncoming electric field relative to the transition dipole of the vibration. This
information is experimentally captured in the line shape of the IR absorption spectrum and can reflect the distribution of electric fields surrounding the probe. This
simplified perspective can result in motional narrowing, where the line shape appears
to be more narrow than the actual distribution of frequencies, yet is informative regarding the dynamics of the surrounding solvent. For example, if the dynamics of
the surrounding solvent are slower than the vibrational frequency of interest the line
shape will be a Gaussian distribution identical to the distribution of the frequencies.
However if self averaging occurs resulting in motional narrowing, the line shape is
Lorentzian, the direct result of a Fourier transformation of an exponential decay.
The linear vibrational spectrum can be in principle be obtained by performing a
Fourier transformation of the quantum mechanical dipole moment time correlation
function (TCF)
Z
I() =
dt expit h(t)
(0)i
(1.2)
where
is the fully quantum mechanical dipole operator. While this approach is
exact, it is computationally intractable to determine the quantum mechanical TCF. A
common approximation is to treat the translational degrees of freedom classically and
replace the quantum mechanical dipole operator with the classical dipole moment.
This oversimplification can result in large errors when calculating relevant frequencies
of interest, when ~ > kT , or when the Born-Oppenheimer potential deviates from a
harmonic approximation. Alternatively, the IR absorption spectra can be computed
from knowledge of the frequency and transition dipole moment trajectories using the
semiclassical fluctuating frequency approximation (FFA),[97]
12
I() =
E
D
Rt
dteit
~ (t)
~ (0)ei 0 d ( ) et/2T1 ,
(1.3)
where h i represents a classical ensemble average, (t) = (t) hi is the fluctuation of the frequency from its average value, hi, and
~ (t) is the transition dipole
moment vector. The FFA expression, 1.3, approximately captures the effects of
inhomogeneous broadening, motional narrowing, rotational broadening, and nonCondon transition dipole moments on the vibrational line shape. The quality of the
resulting spectrum then solely depends on the method of acquiring the frequency
trajectory and transition dipole moment. As further discussed in Chapter 4, the vibrational frequencies for the IR spectra of water in ILs were obtained by connecting
solvent configurations to vibrational frequencies via an empirical relationship. Alternatively, mixed quantum mechanics/molecular mechanics simulations employing
the self-consistent-charge density functional tight binding (SCC-DFTB) were used to
generate the frequencies in Chapter 6 for a tangential project that focused on proton
transfer in aqueous solution.
13
tion and emission fluorescence maximum that is orders of magnitude more intense
than the absorption and fluorescence behavior of imidazolium ILs, so convolution of
the spectrum is not observed.
of the OD stretch frequency of dilute HOD in 1-butyl-3-methyl imidazolium hexafluorophosphate, [bmim][PF6 ], revealed a blue-shifted and a significantly narrowed
vibrational line shape compared to the spectrum of HOD in water. The blue-shift
suggests weaker OD interactions with the ionic environment and is characteristic
of a relatively isolated OD stretch, for example the free OD stretches at a liquid
D2 O/vacuum interface.[117119] The 2D IR measurements monitored spectral diffusion of the OD stretch of HOD in the IL. An important quantity accessible by
both simulation and experiment is the frequency fluctuation time correlation function (FFCF), C(t) = h(t)(0)i, where (t) is the deviation of the frequency
from its equilibrium value, (t) = (t) hi. As a water molecule samples different
molecular environments, the FFCF decays to zero. This can be approximately related
to the spectral diffusion measurements quantified experimentally using the center line
slope (CLS) method.[120, 121] Measurements of the amplitudes and timescales of the
FFCF thus give information about the dynamics of the environment surrounding the
HOD molecule. Two times scales were found: 6.9 2.1 ps and 72 20 ps. The
faster of the two relaxation timescales was attributed to changes in the local structure
of the anions bridged by the water and the subsequent motions of the cations. The
slower relaxation time was assigned to orientational relaxation, though a discrepancy
of approximately one order of magnitude exists between the 72 ps timescale and
the 2.3 ns response in optical heterodyne detected optical Kerr effect experiments in
[bmim][PF6 ].[122]
15
CHAPTER 2
THE MECHANISM OF SOLVATION DYNAMICS IN [emim][BF4 ]
2.1 Introduction
Recall from Chapter 1, that solvation dynamics are measured in time-dependent
fluorescence Stokes shift (TDSS) experiments which employ fluorescent probe molecules
to measure the response of the environment to an instantaneous perturbation of the
charge distribution of the probe molecule.[3941] The experiment begins with an initial laser pulse, v(0) that electronically excites the probe molecule. This excitation
occurs effectively instantaneously, such that the molecular geometry of the probe
molecule is unchanged, but its charge distribution is significantly altered. After the
initial excitation, the solvent environment begins to reorganize to accommodate the
new charge distribution. The reorganization stabilizes the excited electronic state of
the probe relative to its ground electronic state, and subsequent fluorescence, v(t), is
red shifted with respect to the initial fluorescence, v(0). The time scales of the environment reorganization are typically characterized by a solvation response function,
S(t) =
v(t) v()
v(0) v()
(2.1)
where v() is the emission frequency after the environment has completely responded
to the excited state charge distribution of the dye, achieving an equilibrium solvation
structure around the newly formed charges.
Experimental studies of solvation dynamics in imidazolium-based ionic liquids
(ILs) have revealed complex kinetics over a broad range of time scales from fem16
hE(t)E(0)i
,
h(E)2 i
17
(2.2)
where E(t) = E(t) hEi and h i is an ensemble average in the ground electronic state of the probe. Within linear response theory, which will be specifically
examined in Chapter 4, in addition to previous studies have generally found to be applicable to solvation dynamics in ILs at early times in the response,[89] C(t) is equal
to S(t), thus allowing direct comparisons with experiment.[129, 130] During calculations of E(t), the longranged electrostatic interactions between C153 and the IL
molecules were computed with the damped shifted force (DSF) method.[131] The DSF
method is used as an alternative to the traditional Ewald summation technique,[94
96] and facilitates decomposition of the solvation response (see 2.2.2) because it is
based explicitly on a pairwise sum.
(2.3)
where superscript signifies the solvent component of interest. Previous investigations have confirmed empirically that, when linear response theory holds, C(t)
corresponds to the contributions to S(t) from the solvent components (note that S(t)
does uniquely decompose due to the additive property E(t)).[132, 133] Kobrak and
18
Znamenskiy[90] were the first to employ Eq.(2.3) in the context of solvation dynamics
in ILs. They decomposed the solvation response of the solute betaine-30 in 1-butyl3-methyl imidazolium ([bmim]) and hexafluorophosphate ([PF6 ]) over the range from
1 to 5 ps and found that the anion dominates the response on this timescale.
are computed by regarding each relevant IL molecule as a single point charge located
correlation functions for the cations and anions decompose into translational and
rovibrational contributions,
C (t) = Ctrans
(t) + Crovib
(t)
(2.4)
(t)
(t) and Crovib
(t) are computed with Eq.(2.3) using Etrans
where the functions Ctrans
and Erovib
(t) in place of E (t).
19
ters for the bonds, bends, dihedrals, and atomic-centered Lennard-Jones sites were
adopted from the generalized Amber force field (GAFF).[136] Parameters for [BF4 ]
are not available in the GAFF, so these parameters were obtained from Liu et al.[137]
Atomic-centered partial charges for the IL molecules and the ground state of C153
were calculated via the Merz-Singh-Kollman[138] analysis of the electron density of
the optimized geometry of the molecules obtained with density functional theory
(DFT) with a B3LYP functional and the aug-cc-pVDZ basis set. The change in
the partial charges for C153 upon electronic excitation were calculated and validated
previously by Cinacchi et al.[1] thus the excited state partial charges for C153 are
obtained by simply adding these changes to the computed ground state charges. In
the MD simulations the long-ranged electrostatic interactions were computed with
the particle-mesh Ewald summation method with a 15
A real-space cutoff.[94, 139]
This same cutoff distance was utilized when computing interactions between LennardJones sites.
Since imidazolium-based ILs are known to exhibit slow (nanosecond) relaxation
dynamics, we employed a rigorous equilibration protocol before performing the production run simulations from which the solvation response function was calculated.
Following an initial period of minimization, the temperature was slowly raised from
0 K to 300 K over a period of 200 ps. This was followed by a 4 ns simulation in the
NPT ensemble (300 K and 1 atm) using a Nose-Hoover thermostat and barostat.[140]
The size of the simulation box was isotropically scaled to reflect the average density
and was then simulated in the NVT ensemble for 1 ns at 300 K, the temperature
was raised to 600 K over 1 ns to destroy any pseudo-stable ionic cages that may
have formed. Next, the temperature was reduced back to 300 K in 1 ns, followed by
the NVT simulation for 1 ns at constant temperature of 300 K. The final velocities
were scaled to 300 K and a pre-production NVE simulation was performed for 11
ns. Production-runs (comprising a total of 5.015 s) were performed in the NVE
20
in the regime beyond 10 ps. To quantify the differences in the long-time decay between experiment and theory, both solvation response curves were fit with a stretched
exponential function, A exp((t/ ) ), in the range from 10 ps to 1 ns (Table 2.1 and
Figure 2.2). A stretched exponential is ideal over this range as it captures the superposition of an indefinite number of single exponential decays all weighted by a
distribution of relaxation times.[144]
The time constant, , is shorter in the theoretical result (81.4 ps) than in the
experiment (115.7 ps). It has been empirically established that the long-time decay of
the solvation response in imidazolium-based ILs is viscosity dependent.[7, 65, 69, 80]
Thus, the slightly too large self-diffusion constants for the molecules in the neat
[emim][BF4 ] simulation Section 2.2.4 are a likely culprit for the slightly too fast longtime decay of the solvation response. While it is beyond the scope of the present study,
it might be possible to utilize the experimental solvation response data to further
refine the dynamical properties of the IL force-field via the empirical charge scaling
factor discussed in Section 2.2.4 and Chapter 3. While modest discrepancies in the
long-time decay exist, the calculated solvation response captures the complex kinetic
behavior of the experimental measurement, thus validating the simulations directly
with experiment, and we will now proceed to further analyze the simulations to
uncover the molecular mechanisms responsible for solvation dynamics in [emim][BF4 ].
Figure 2.3 shows the decomposition of the total calculated solvation response of
C153 in [emim][BF4 ] into contributions from the anions, cations, and internal motions
of the C153 solute. It is immediately apparent that the anions dominate the solvation
response. Not only is the anion contribution substantially larger than that of the
cations or C153 for all time scales, it also mimics closely the characteristic shape of
the total response curve. The internal motions of the C153 solute do not contribute
to the decay of the solvation response (i.e. the C153 component of the response
22
23
Figure 2.2. Fits of the calculated (black) and experimental (green) solvation
responses of C153 in the IL [emim][BF4] to a stretched exponential
function, A exp((t/ ) ), in the time range between 10 ps and 1 ns. The
data are shown as filled circles, while the fits are lines. The quality of the
fits in terms of the correlation coefficient, r2 , are excellent: r2 = 0.9987 for
the theoretical data and r2 = 0.9983 for the experimental data.
24
25
TABLE 2.1
PARAMETERS FOR A STRETCHED EXPONENTIAL FIT
Experiment
Theory
0.38
0.32
(ps)
115.7
81.4
0.55
0.74
Parameters for a stretched exponential, A exp((t/ ) ), fit to the calculated and experimental solvation response functions in the range from 10 ps to 1 ns.
g(r), for the center-of-mass of the cations and anions relative to the center-of-mass
of the C153 solute. The most striking feature is the dramatic enhancement of [emim]
cations in the vicinity of the C153 molecule, represented by the pronounced peak near
4
A and the corresponding depletion of [BF4 ] anions close to C153. The preferential
solvation of C153 by [emim] is perhaps not surprising, since the molecules can align
their flat surfaces and take advantage of favorable stacking interactions. While
the radial distribution function shown in Figure 2.4 does not give a full characterization of the three-dimensional solvent structure around the non-spherical C153 solute,
it does indicate that the [emim] cations are, on average, more proximal to the C153
solute than the [BF4 ] anions. This observation is consistent with previous studies of
the three-dimensional solvent structure around aromatic compounds in imidazolium
ILs.[147, 148] The observation of preferential solvation creates a conundrum for understanding solvation dynamics in [emim][BF4 ]. Conventionally, solvation dynamics
is dominated by molecules close to the fluorescent dye molecule. In this case, however, the anions, which have been implicated as the dominant player in the response
dynamics (Figure 2.3), are generally further away from the C153 dye molecule than
the cations. Before we resolve this issue, it is worth noting that the observation of
preferential solvation has broader implications. In most experiments that employ an
exogenous spectroscopic probe molecule, the general assumption is that the presence
of the solute does not greatly alter the native structure and dynamics of interest.
In this case, the C153 molecule is apparently inducing structure in the IL. This implies that there is some ambiguity as to whether the experiment is really measuring
dynamics that are native to the neat IL. Preferential solvation effects could also be
relevant to the interpretations of other experiments on IL structure and dynamics.
To determine which specific motions of the [emim] and [BF4 ] molecules are most
relevant to solvation dynamics, we further decomposed the anion and cation solvation responses into contributions from translations and rovibrations (Figure 2.5).
27
Figure 2.4. The radial distribution function, g(r), for C153-[emim] and
C153-[BF4 ] pairs, where r is defined as the distance between the
center-of-mass positions of the relevant pair of molecules.
28
Focusing first on the [BF4 ] anions the results are unambiguous: translational motions of the anions dominate the total response, whereas [BF4 ] rovibrational motions
are negligible. Note that the shape of the anion translational decomposition nearly
perfectly mimics the total solvation response. Since the [BF4 ] molecule is symmetric
and possesses no permanent dipole moment it is not surprising that its rovibrational
motions do not affect the solvation dynamics. However, since solvation dynamics in
conventional polar liquids is governed mostly by rotational motions of the solvent,
the central importance of the translational motions of [BF4 ] to the solvation response
of C153 in [emim][BF4 ] is unusual and warrants further investigation. The cations
also exhibit unusual and interesting behavior in Figure 2.5. The translations of the
cations are also a significant contributor to the total solvation response (but still significantly less than the anion translations), however these contributions are largely
offset by the cation rotations, which are uniformly negative in sign on all time scales.
Negative values of the cation rotational contribution to the total solvation response
indicate that these motions are actually counterproductive, on average, to stabilizing
the excited state charge distribution of the C153 solute.
The final unresolved issue for obtaining a complete view of the mechanism of
solvation dynamics in the [emim][BF4 ] IL is to determine which specific translational
motions of the [BF4 ] anion are relevant. For this we computed the residence-time
correlation function (RTCF) for the anions and cations in the first solvation shell of
the C153 solute, hn(0)n(t)i, where n(t) = 1 if the molecule of interest is in the first
solvation shell and n(t) = 0 if it is not (Figure 2.6). For the purposes of the RTCF
calculation the first solvation shell was defined as any molecule whose center-of-mass
lies within 5.6
A of the center-of-mass of the C153 probe. 5.6
A was chosen because
it is the first minimum of the C153-[emim] radial distribution function. The RTCF
describes the time scales for molecules, either anions or cations, to enter or leave the
first solvation shell of the solute. The RTCF for the anion is generally similar to
29
Figure 2.5. The solvation responses of [emim] (blue) and [BF4 ] (red)
decomposed into contributions from translational (solid) and rovibrational
(dashed) motions. For reference, the total solvation response minus the
contribution from the internal motions of the C153 solute is also shown
(black).
30
Figure 2.6. The residence-time correlation function (RTCF) for the anions
and cations in the first solvation shell of the C153 solute. The first
solvation shell was defined as any molecule whose center-of-mass lies within
5.6
A of the center-of-mass of the C153 probe.
31
the solvation response. It appears to exhibit the same unusual kinetic profile as the
solvation response, which is suggestive that these anionic translational motions are
relevant for the response. In contrast, the RTCF for the cations is significantly slower
than the anions and its shape is qualitatively different from the solvation response.
The time scales for the decay of the anion RTCF are similar, although clearly slower,
than the solvation response. However, the difference in the times scales is likely due to
the somewhat arbitrary definition of the solvation shell. Changing the cutoff distance
for the solvation shell alters the time scales for the RTCF decay of both anions and
cations, but the qualitative profiles are unchanged (data not shown). The results in
Figures (2.42.6) support a solvation dynamics mechanism in [emim][BF4 ] where the
translational motion of the anions into and out of the first solvation shell of the C153
probe molecule potentially play an important role.
2.4 Summary
Extensive MD simulations have revealed the detailed molecular motions responsible for solvation dynamics of C153 in the imidazolium-based IL [emim][BF4 ] (Figure
2.7). Solvation dynamics in liquids generally involves collective motions of the solvent
environment in the vicinity of the fluorescence probe molecule. In this case, however,
we have identified a particular molecular motion that appears to be especially relevant to solvation dynamics in [emim][BF4 ], namely the translational motion of the
[BF4 ] anion into and out of the first solvation shell of C153. This proposed mechanism is consistent with a number of previous simulation studies that have implicated
translational motions and/or motions of the anions as being especially relevant to
solvation dynamics in imidazolium-based ILs.[82, 86, 8890] The MD simulations
have also revealed that the IL forms a specialized structure around the C153 solute,
in which the first solvation shell is enriched in [emim] while the second solvation
shell is enriched in [BF4 ]. An important question remains for future studies: how
32
33
general is this anion-translation mechanism? It seems likely that other imidazoliumbased ILs, whose cations can preferentially solvate dyes with fused ring structures,
will exhibit this mechanism. However, as one deviates from the structural motifs
of the C153/[emim][BF4 ] system, new solvation dynamics mechanisms could emerge.
This presents both challenges and opportunities for the theoretical and experimental
communities interested in designing ILs with properties selectively tuned for specific
applications.
34
CHAPTER 3
SIMULATIONS OF THE SOLVATION RESPONSE IN A SERIES OF IONIC
LIQUIDS
3.1 Introduction
In the previous chapter microsecond-length molecular dynamics (MD) simulations of coumarin 153 (C153) in 1-ethyl-3-methyl imidazolium tetrafluoroborate,
[emim][BF4 ], were performed to reveal the molecular-level mechanism for solvation
dynamics. In that particular system it was the translational motion of the [BF4 ] anion
into and out of the first solvation shell of C153 that dominated the solvation response.
Given the sensitivity of certain properties to variations in the cation and anion constituents in the IL[9, 2125], it is necessary to understand if this anion-translation
mechanism can be generalized to other imidazolium-based ILs. This chapter presents
calculations of the solvation response of C153 in a series of imidazolium-based ILs
comprised of cations and anions seen in Figure 3.1. Two cations, 1-butyl-3-methyl imidazolium, [bmim], and 1-ethyl-3-methyl imidazolium, [emim], were paired with four
different anions, tetrafluoroborate, [BF4 ], dicyanamide, [DCA], trifluoromethanesulfonate, [TfO], hexafluorophosphate, [PF6 ], to create five unique systems, [emim][BF4 ],
[bmim][BF4 ], [bmim][DCA], [bmim][PF6 ], and [emim][TfO] allowing a direct comparison to experiment. Studying this series where size, shape, and charge distribution of
the cations and anions varies is helpful to determine if any trends or generalizations
regarding the solvation mechanism are present.
Additionally, this chapter investigates the effects of charge scaling. Transport
properties such as the mean-square displacement (MSD), diffusion coefficients, and
35
Cations
Anions
[bmim]
[BF4]
[PF6]
[emim]
[DCA]
[TfO]
36
viscosity are all affected by modifications to the charges. The accuracy of a molecular
dynamics simulation is dependent on the proper selection of the force field parameters. Force fields are an approximation to the intra- and inter-molecular interactions
that attempt to capture the properties of molecules accurately and efficiently over a
range of conditions. A force field contains three kids of parameters that determine
bonded interactions, electrostatics, and short range interactions. Bonded parameters are generally calculated from quantum mechanics, whereas electrostatics and
short-range interactions are more difficult to parametrize. Accurately representing
this interplay between long-range and short-range interactions is key to achieving a
correct description of the system, and it truly matters how the force field deals with
charge transfer and polarization. Some force fields are more general, such as OPLS,
GAFF, or CHARMM, meant to be transferable over a range of molecules and temperatures while others are created and parameterized to match specific experimental
properties.
Classical, or non-polarizable, force fields use static partial charges for each atomic
site to model the electrostatic interactions. In IL systems, non-polarizable force
fields typically underestimate dynamic and transport properties due to a neglect
of the electronic polarization and charge transfer effects present in the condensed
phase. Ideally using a fully polarizable force field would adequately capture the
movement of electron densities, and various studies have examined the inclusion of
polarizability.[81, 143, 149151] Polarizable models consistently show faster translational and rotational relaxations, higher self-diffusion and conductivity, and lower
shear viscosity when compared to non polarized models. This is a consequence of
a weakening of the long-range interactions caused by enhanced screening. However,
due to the sluggish dynamics and the the long timescales required for accurate descriptions of solvation dynamics calculations, simulating hundreds of molecules in a
fully polarizable model for microseconds is computationally prohibitive.
37
Utilizing fixed charges in a non-polarizable force field requires careful insight into
how one deals with charge transfer and polarization. While not modeling the atomic
sites as being explicitly responsive to their local environment, fixed-charge force fields
accomplish an effective representation by scaling the charges of the molecules and
using existing generalized force fields, or undergo a complete reparameterization of the
short-range interactions and keep the unit charges 1. Adopting the latter method,
Koddermann et al.[152] showed that through reparameterization and matching the
experimentally derived observables (density, self-diffusion coefficients, and rotational
correlation dynamics) they were able to reproduce viscosity, the heats of vaporization
and dynamic properties maintaining full unit charges on all molecules. While this
force field is transferable to imidazolium cations with various alkyl chain lengths, it
requires dynamical properties as inputs to fit these short range parameters, which
presents a difficulty as these experiments for a range of cation and anion pairs are
sparse.
Reducing the net charges, entertainingly referred as Poor mans polarization,[143]
is grounded in electronic structure calculations. A number of studies performing ab
initio calculations of non-isolated IL ions revealed the net charges are reduced due to
charge transfer and polarization.[153158] In principle, charge transfer occurs when
the charge density is shifted from one ion to another ion via orbital overlap. Quantifying this effect was carried out when a systematic study involving XPS, NMR, and
corroborating evidence from DFT calculations determined significant charge transfer
and polarization are present in these ILs.[103] Taken together, a reduced point charge
is representative of this screened partial charge. In Section 3.4 the effects of varying
the overall scaled charges on the dynamics in ILs are discussed.
38
3.2 Methodology
3.2.1 Decomposition of the Solvation Response
Recall the total solvation response can be decomposed into contributions from the
different constituents present in the liquid. Such decompositions are made possible
because of the additive nature of the solute interaction energy, E(t) = E (t),
where E (t) is the solute interaction energy with solvent component , in this case
the anions, cations, and intramolecular electrostatic interactions within the probe
itself. Unfortunately, there is not a unique decomposition of C(t) simply based on
expressing E (t) as a sum. However, one decomposition strategy is formally compatible with linear response theory,[90, 124, 132]
C (t) =
hE (t)E(0)i
,
h(E)2 i
(3.1)
where superscript signifies the solvent component of interest. Note that could
also correspond to other components such as rotations and translations of cations
and anions, thus allowing further insight.
[bmim][BF4 ],[bmim][PF6 ], and [bmim][DCA], = 0.84. The validity of this assumption is examined below in Section 3.4.1. For the analysis of charge scaling, identical
systems were created however the net charge was scaled appropriately. All of the
molecules were modeled as fully flexible, except for covalent bonds containing hydrogen which were fixed at equilibrium lengths using the SHAKE algorithm.[135] The
force field parameters for the bonds, bends, dihedrals, and atomic-centered LennardJones sites for [BF4 ] and [PF6 ] were obtained from Liu et al.[137], while the parameters for [DCA] were taken from Lopes et al.[159] For C153, [emim], [bmim], and [TfO],
parameters were adopted from the generalized Amber force field (GAFF).[136] All
atomic-centered partial charges for the IL molecules and the ground state of C153
were derived using the Merz-Singh-Kollman[138] scheme to interpret the electron
density of the optimized geometry of the molecules obtained with density functional
theory (DFT) with a B3LYP functional and the aug-cc-pVDZ basis set. The change
in the partial charges for C153 upon electronic excitation were calculated identical
to Chapter 2. In the MD simulations the long-ranged electrostatic interactions were
computed with the particle-mesh Ewald summation method with a 15
A real-space
cutoff.[94, 139] This same cutoff distance was utilized when computing interactions
between Lennard-Jones sites. The equivalent equilibration protocol was employed
whereby each system undergoes a total of 22 ns of minimization, NPT, NVT, and
NVE ensemble simulations explicitly laid out in Chapter 2. All production-runs were
performed in the NVE ensemble with a 2 fs integration time step and a collection
resolution of 10 fs for trajectories 2.0 s long.
Simulations of the pure ILs were performed for 100 ns to validate our force field
and charge scaling parameter. Determining a reliable a self-diffusion coefficient requires considerable amounts of simulation time, though to ensure sufficient convergence, multiple checkpoints from the trajectory were used as starting points in the
calculation. Using the Einstein relation, limt MSD = 6Dt, in the linear range of
40
TABLE 3.1
SELF-DIFFUSION COEFFICIENTS FROM MD SIMULATIONS
System
D+ [sim]
[bmim][BF4 ]
0.84
1.7
[bmim][DCA]
0.84
[bmim][PF6 ]
[emim][TfO]
[emim][BF4 ]
[sim]
[lit]
[lit]
D+
Ref
1.2
1.4
1.3
[161]
1.7
2.0
0.4
0.5
[160]a
0.84
0.6
0.3
0.8
0.6
[162]
0.80
3.0
1.3
1.1
1.6
[81]a
0.84
1.9
0.9
0.80
8.1
5.5
5.0
4.2
[163]
1.0
0.3
0.2
0.80ring
6.8
4.9
Polarizable MD simulation results. The ion self-diffusion coefficients D+/ (in units
of 1011 m2 /s) from MD simulations along with literature values for the IL systems.
The net unit charge of the cations and anions is given by .
0.1 1000 ps, self-diffusion coefficients were calculated (Table 3.1). In all cases the
simulated ILs compare favorably with experiment, albeit predicting faster dynamics.
In the absence of experimental data for [bmim][DCA] and [emim][TfO], transport
properties calculated using parameters from polarizable force fields [81, 160] indicate our MD simulations are in reasonable agreement. See Section 3.4, in particular
Subsection 3.4.1, for a discussion regarding the implications of charge scaling on the
dynamic properties.
41
43
44
contributions from the anions (red), cations (blue), and internal motions of the C153
solute (purple). In all cases the anions dominate the solvation response. Not only is
the anion contribution substantially larger than that of the cations or C153 for all
time scales, the anions are responsible for the the characteristic shape of the total
response curve. The internal motions of the C153 solute do not contribute to the
decay of the solvation response (i.e. the C153 component of the response is generally
flat).
The decomposition results indicate the anions play a particularly important role
in determining the solvation response. Further insight regarding the role of the anions
in the solvation response, is gained by analyzing the structure of the IL in the vicinity of the C153 probe. Shown in Figure 3.8 are radial distribution functions, g(r),
for the center-of-mass of the cations and anions relative to the center-of-mass of the
C153 solute, including the results from [emim][BF4 ] reported in Chapter 2. Immediately apparent is the proximity at which the relatively larger imidazolium cations
are to the C153 molecule compared to the smaller, mostly spherical anions. The
non-spherical anion, [DCA], shows a small enhancement near 4
A before mimicking
similar charge ordering seen in the other ILs. While the radial distribution function
shown in Figure 3.8 does not give a full characterization of the three-dimensional solvent structure around the non-spherical C153 solute, it does indicate that the cations
are, on average, closer to the C153 solute than the anions. This observation is consistent with previous studies of the three-dimensional solvent structure around aromatic
compounds in imidazolium-based ILs,[147, 148] though confirms that despite the diversity of the molecular environments in these ILs, preferential solvation of C153 by
the imidazolium-based cations is persistent. Given the favorable stacking interactions between C153 and the imidazolium ring and the heterogeneous nature of
these systems,[5464] it is conceivable a degree of preferential solvation is present.
Preferential solvation as first understood in mixtures of polar and non-polar solvents
45
46
47
48
49
Cations
Anions
Figure 3.8. The radial distribution function, g(r), for C153-[cation] and
C153-[anion] pairs, where r is defined as the distance between the
center-of-mass positions of the relevant pair of molecules.
50
was first described in terms of dielectric enrichment[164, 165] where the solute is
surrounded by solvent molecules to form an associated complex in thermodynamic
equilibrium. Studies examining the effects of preferential solvation of C153 in tolueneacetonitrile and toluene-methanol mixtures[166] and more recently in IL-surfactant
solutions[167] have highlighted the implications of these non-ideal systems. In most
experiments that employ a spectroscopic probe molecule, the general assumption is
that the presence of the solute does not alter the native structure and dynamics of
interest. Figure 3.8 reveals the C153 molecule is apparently inducing structure in
the ILs. This suggests that there is some ambiguity as to whether the experiment is
really measuring dynamics that are native to the neat IL.
Further decomposition of the component solvation responses in Figures 3.9-3.12
identifies specific motions, translations and rovibrations, of the cation and anion
molecules necessary for effective charge accommodation. The results are unambiguous: translational motions of the anions (solid red) dominate the total response for
all imidazolium-based ILs studeied here, whereas anion rovibrational motions (red
dashed) are negligible, or slightly negative in the case of [bmim][DCA]. The translations of the cations (solid blue) are also a significant contributor to the total solvation response, however these contributions are offset by the cation rotations, which
are negligible or negative in sign on all time scales. Negative values of the [DCA]
and cation rotational contribution to the total solvation response indicate that these
motions are actually counterproductive to stabilizing the excited state charge distribution of the C153 solute.
Solvation dynamics in conventional polar liquids is governed mostly by librational and rotational motions of the solvent molecules proximal to the fluorescent
dye molecule. The results of the solvation response decomposition presented in Figures 3.4-3.12 indicate the translational motions of the anions are essential to the
solvation response of C153 in imidazolium-based ILs. To determine which specific
51
Figure 3.9. The solvation responses of [bmim] (blue) and [BF4 ] (red)
decomposed into contributions from translational (solid) and rovibrational
(dashed) motions. For reference, the total solvation response is also shown
(black).
52
Figure 3.10. The solvation responses of [bmim] (blue) and [DCA] (red)
decomposed into contributions from translational (solid) and rovibrational
(dashed) motions. For reference, the total solvation response is also shown
(black).
53
Figure 3.11. The solvation responses of [bmim] (blue) and [PF6 ] (red)
decomposed into contributions from translational (solid) and rovibrational
(dashed) motions. For reference, the total solvation response is also shown
(black).
54
Figure 3.12. The solvation responses of [emim] (blue) and [TfO] (red)
decomposed into contributions from translational (solid) and rovibrational
(dashed) motions. For reference, the total solvation response is also shown
(black).
55
Figure 3.13. The residence-time correlation function (RTCF) for the anions
and cations in the first solvation shell of the C153 solute. The first solvation
shell was defined as any molecule whose center-of-mass lies within the first
solvation shell, defined as the first minimum of the cation-C153 g(r).
56
translational motions of the anions are relevant we computed the residence-time correlation function (RTCF) for the anions and cations in the first solvation shell of
the C153 solute, hn(0)n(t)i, where n(t) = 1 if the molecule of interest is in the first
solvation shell and n(t) = 0 if it is not (Figure 3.13). For the purposes of the RTCF
calculation the first solvation shell was defined as any molecule whose center-of-mass
lies within the first solvation shell, defined as the first minimum of the cation-C153
g(r) (top panel in Figure 3.8). The RTCF reports on the time scales for molecules,
either anions or cations, that enter or leave the first solvation shell of the solute. The
RTCF for the anions share the characteristic shape of the solvation response, which
is suggestive that these anionic translational motions are relevant for the response.
In contrast, the RTCF for the cations is significantly slower than the anions and
its shape is qualitatively different from the solvation response. The time scales for
the decay of the anion RTCF are similar, although clearly slower, than the solvation
response. However, the difference in the times scales is likely due to the somewhat
arbitrary definition of the solvation shell. The results in Figures (3.83.13) support
a solvation dynamics mechanism in ILs where the translational motion of the anions
into and out of the first solvation shell of the C153 probe molecule potentially play
an important role.
57
58
59
increased the self-diffusion coefficients from 0.31011 m2 /s for [emim] and 0.21011
m2 /s for [BF4 ] with full unit charges to 8.1 1011 m2 /s for [emim] and 5.5 1011
m2 /s for [BF4 ]. It is conceivable that the alkyl chain of the cation will play a minor
role in the polar regions of increased charge density, and applying a uniform charge
scaling factor to the entire molecule is too drastic. In fact, if the atomic partial
charges on the imidazolium ring are scaled while the charge density on the alkyl chain
is unchanged the computed self-diffusion coefficients, 6.8 1011 m2 /s for [emim] and
4.9 1011 m2 /s for [BF4 ], compare more favorably with experiment (5.0 1011
m2 /s and 4.2 1011 m2 /s).[163]
61
solvation response utilizing the scaled charges of 0.825 only modestly improves the
long time dynamics, relative to experiment.
The unsophisticated approach of tuning the partial charges of the molecules as
a means to improve agreement with experimental measurements of the solvation
response is not ideal. To be thoroughly correct, a full reparameterization of the force
field is necessary to adequately describe the complicated combination of molecular
interactions observed in solvation dynamics.
3.5 Summary
The calculated solvation response of C153 in a series of imidazolium-based ILs,
[emim][BF4 ], [bmim][BF4 ], [bmim][DCA], [emim][TfO], and [bmim][PF6 ] identify a
general solvation mechanism. The particular molecular motion that appears to be
especially relevant to solvation dynamics in imidazolium-based ILs are the the translational motions of the anions into and out of the first solvation shell of C153, regardless
of the composition of the IL. It is conceivable postulate that as one deviates from the
structural motifs whereby the cations cannot preferentially solvate dyes with favorable
aromatic interactions, new solvation dynamics mechanisms will emerge. Investigating the impacts of charge scaling revealed the linear dependence of the self-diffusion
coefficient on the effective scaling parameter. Charge-scaled models are able to reproduce the complexities of the solvation response function, and are ideally suited to
reproduce collective properties where the use of polarizable models is impractical.
62
CHAPTER 4
REGARDING THE VALIDITY OF LINEAR RESPONSE THEORY IN
SOLVATION DYNAMICS SIMULATIONS OF IONIC LIQUIDS
4.1 Introduction
Observing the evolution of solvent reorganization in the vicinity of an excited
probe molecule provides unique insight into molecular interactions responsible for
accommodating a charge perturbation. In particular, discerning these molecular
mechanisms is important to understanding the role of solvents in charge-transfer
reactions whose kinetic rates are influenced by solvent reorganization.[38] Central
to the study of solvation dynamics is linear response, which makes the assumption
that the dynamics of a system responding to a nonequilibrium state are equivalent
to the response to thermal fluctuations identical in amplitude and frequency in an
equilibrium system.
Time dependent fluorescence Stokes-shift (TDSS) measurements investigating
these solvation dynamics rely on an ultrafast laser pulse with energy hv(0), that
electronically excites a fluorescent probe molecule such as Coumarin-153 (C153),
4-aminophthalamide (4-AP), or PRODAN. This excitation is essentially occurring
instantaneously following the Franck-Condon principle, where the molecular geometry of the probe molecule is unchanged, but the charge distribution is significantly
altered such that a large change in the dipole is achieved. The subsequent fluorescent
emission of the probe, v(t), is continuously shifted to longer wavelengths over time,
as the solvent molecules reorganize to establish new equilibrium positions relative
63
to the new charge distribution. TDSS experiments monitor this temporal evolution
with a time dependent solvent response function,
S(t) =
v(t) v()
v(0) v()
(4.1)
where v() is the emission frequency after the environment has completely responded
to the excited state charge distribution of the probe.[3941] Linear response theory
equates the nonequilibrium response function S(t) to the equilibrium time correlation
function (TCF), C0(1) (t), of the fluctuations in the solvent effect on the electronic
energy gap,[129, 169]
S(t)
= C0(1) (t) =
hE(0)E(t)i0(1)
h(E)2 i0(1)
(4.2)
where E(t) = E(t) hEi0(1) and h...i0(1) is an ensemble average with the
probe molecule modeled in the ground or excited electronic state, respectively. Here
E(t) = Ee (t) Eg (t) the difference in the interaction energy of the probe molecule
with its environment for the excited (Ee ) and ground (Eg ) electronic states. An
important criteria for the validity of linear response theory is that the time-dependent
distribution of E(t) be adequately described by a Gaussian distribution.[130, 170]
Deviations from linear response occur when the electronic transition of the probe
molecule undergoes significant change in magnitude, size, or when the excitation
alters the solvation structure in such a way that it is no longer similar to ground
state fluctuations, e.g. altering the hydrogen bonding capabilities.[41, 128]
In Chapters 2 and 3, we postulated the solvation mechanism in imidazoliumbased ILs is dominated by translational movements of anions into and out of the
first solvation shell surrounding the probe molecule.[171] Our calculations compare
favorably with experiment, though they rely on the validity of linear response in order
to appropriately characterize the system. A study using all-atom molecular dynamics
64
simulations which included polarization effects calculated C0 (t) and C1 (t) for three
ILs over the entire duration of the response, however no direct comparison to S(t)
was achieved due to the significant computational costs.[81] Simulations explicitly
comparing the nonequilibrium response S(t) and C(t) in ILs were performed by Shim
et al. using a diatomic and benzene-like probes and united-atom representations of
the IL molecules, where they found sufficient similarity between S(t) and C(t).[89]
While their findings have been used as justification for applying linear response theory
in solvation dynamics simulations of ILs, due to computational limitations at that
time, the simulations only calculated the solvation response out to 2 ps. Given
experimental evidence that the solvation response is known to persist for nanoseconds
in ILs[2, 3], examining the applicability of linear response theory over the entire
relaxation timescale is warranted.
S (t) =
E (t) hE ()i1
hE (0)i0 hE ()i1
(4.3)
where the overbar represents an average over nonequilibrium trajectories and the
superscript signifies the solvent component of interest. Calculating the component
contributions to C (t) in a way that is formally compatible with linear response
theory is given as,[124, 126, 132, 169]
hE (t)E(0)i
C (t) =
.
h(E)2 i
(4.4)
This formalism importantly retains the same amount of information without invoking
67
68
any cross-correlations that are often incapable of providing a clear molecular mechanism for solvation dynamics. Unfortunately, a commonly reported decomposition
scheme utilizes binomial multiplication providing auto- and cross-correlation terms
that are inadequate at identifying distinct components responsible for solvation.
The two alternative decomposition schemes applied to C0 (t) are shown in Figure
4.2. The top panel contains the auto- and cross-correlation functions contrasted with
the proper decomposition for a complex perturbation in the bottom panel. The autocorrelation of the anion-anion component in top panel shows the dominance of the
anion-anion contribution (red) followed by the cation-cation (blue) auto-correlation
term. The dashed lines represent the cross-correlation terms (anion-cation, aniondye, and cation-dye), which are mostly negligible, with exception to the anion-cation
cross-correlation contribution. While this does contain interesting information about
the interactions between components, this unnecessarily complicates the interpretation of the solvation mechanism by indicating there is a degree of anti-correlation
between the constituents, without exposing the exact intricacies necessary to understand solvation. It is possible to remove the ambiguity by employing Eq. 4.4 to
determine the contribution from each component relative to the total response, as
seen in the bottom panel of Figure 4.2. It is then straightforward to understand
the importance of the anions in solvating C153 without any obscure cross-correlation
terms. Using the latter decomposition scheme, Figure 4.3 presents the component
solvation response for anion (top) and cation (bottom) contributions for nonequilibrium S(t) (black) and equilibrium C1 (t) (red), and C0 (t) (green). The decompositions
for C0(1) (t) that are consistent with S (t), fitting with linear response theory.
The solvation response functions for the anions and cations can be further decomposed into contributions resulting from their respective translational and rovi
brational motions. The translational contribution, Etrans
, to E for the cations
and anions are computed by regarding each relevant IL molecule as a single point
69
70
Figure 4.3. The normalized solvation response decomposed into anion (top)
and cation (bottom) contributions for nonequilibrium S(t) (black) and
equilibrium C1 (t) (red), and C0 (t) (green) from 50 fs to 1 ns.
71
Figure 4.4. The normalized solvation responses of S(t) (black), C1 (t) (red),
and C0 (t) (green) decomposed into contributions due to translational
(solid) and rovibrational (dashed) motions.
72
Erovib
, to E is then obtained as the difference, Erovib
= E Etrans
. With
these definitions, the correlation functions for the cations and anions decompose into
translational and rovibrational contributions,
C (t) = Ctrans
(t) + Crovib
(t)
(4.5)
and Erovib
(t) in place of E (t).
74
CHAPTER 5
A MOLECULAR DYNAMICS INVESTIGATION OF THE VIBRATIONAL
SPECTROSCOPY OF ISOLATED WATER IN AN IONIC LIQUID
5.1 Introduction
Our understanding of water-ion interactions is derived primarily from studies of
dilute aqueous salt solutions in which the ions are fully hydrated and water-water
interactions are perturbed but still prevalent. Studying water at dilute concentrations
in an ionic liquid (IL) reverses this scenario; the water is isolated in a sea of ions and
the water-water interactions are negated. The water/IL system provides a unique
opportunity to investigate the dynamics of water in a highly electrolytic environment.
Moreover, the isolated water molecule can serve as a reporter of the structure and
dynamics of the IL.
Despite their promise as environmentally friendly solvents and in clean and renewable energy applications,[7, 1017] widespread industrial adoption of many ILs
is plagued by their large viscosities.[174] While impurities such as water are known
to alter the physical properties and chemical reaction rates in hygroscopic ILs,[20,
175, 176] the addition of this cosolvent is gaining in popularity as a means to reduce
viscosity.[177] Thus, understanding the behavior of water in ILs and how water alters
the properties of ILs has important practical implications.
Many ILs are hygroscopic and complete removal of water is nearly impossible.[178
180] A variety of experimental[5458] and computational[5964] studies have aimed to
understand the influence of water on the properties of ILs. These studies suggest that
75
some ILs have nanoscale structuring with polar and nonpolar regions.[60, 61, 181
186] As the water concentration in these ILs increase, the polar domains collapse with
the formation of larger water clusters stabilized by a hydrogen-bond network.[60, 187]
Previous work examining isolated water in ILs determined a water molecule is bridged
by two anions in an IL, existing in an A HOH A complex. As a result of
this proximity, the anions were assumed to be most responsible for influencing the
OH stretch frequency.[112114] Investigations varying the lengths of the cation alkyl
chains in imidazolium-based ILs suggest the chains do not have an influence on the
OH stretching frequency.[112, 115]
X-ray spectroscopy, NMR, and vibrational spectroscopy have been used to understand structure in bulk ILs. [25, 101, 102, 104] Ultrafast two-dimensional infrared
(2D IR) spectroscopy measurements of ILs have the potential to elucidate important dynamical motifs that differ from conventional solvents. 2D IR spectroscopy
has already proven itself as a powerful technique for investigating the structure and
dynamics of liquids by monitoring the response of a vibration to the evolution of its
local environment, a process called spectral diffusion. The frequencies of vibrational
reporters are exquisitely sensitive to changes in their local environment, particularly
to changes in electrostatics, hydrogen bonding, and chemical processes. For example, the OH and OD stretch frequencies of HOD are known to depend on hydrogen
bonding: an increase in hydrogen-bond strength red-shifts the OH and OD stretch
vibrational frequencies. The inhomogeneous IR absorption line shape of liquid water
reflects the range of different hydrogen bonding environments present. [105107] The
spectral diffusion time scales revealed by 2D IR have been shown to directly relate
to hydrogen bond rearrangement processes in liquid water.[108111]
Recently, the dynamics of HOD isolated in an IL was investigated with vibrational
spectroscopy.[116] The linear IR absorption spectrum of the OD stretch frequency
of dilute HOD in 1-butyl-3-methyl imidazolium hexafluorophosphate, [bmim][PF6 ],
76
77
EOD = rOD
N
X
qi riD
i=1
2
riD
(5.1)
where rOD is the unit vector along the OD bond, riD is the distance between charge i
and the D atom, and riD is a unit vector between site i and the D atom. For calculations of EOD the long-range electrostatic interactions were corrected with the damped
shifted force (DSF) method.[131] One motivation for utilizing the DSF method rather
than traditional Ewald summation techniques[9496] is that DSF treats the interactions as a pairwise sum, thus lending itself to straightforward decomposition in terms
of the contributions of the anions and cations in the IL.
The empirical relationship that relates the OD vibrational stretch frequency,
78
OD , to EOD was developed by Lin, Auer, and Skinner in HOD for aqueous NaBr
solutions[192]
OD = 2762.6 cm
cm1
cm1
2
3640.8
Eef f 56641
Eef
f.
au
au2
(5.2)
Here an effective electric field, Eef f , was introduced to account for the blue-shifts in
the OD stretch frequency observed experimentally with increasing salt concentrations,
(5.3)
where a and b are empirical parameters, 0.81379 and 0.92017, respectively. EH2 O ,
Ecat , and Ean are contributions to EOD from water, cations, and anions, respectively. This spectroscopic map was designed to be applicable for all aqueous salt
concentrations, and when no ions are present the map is conveniently appropriate for
HOD in H2 O. The unequal weighting of the contributions for the cations and anions
reproduces the smaller OD frequency shifts observed in electrolyte solutions.
Because non-Condon effects are known to be important in the vibrational spectroscopy of water,[191] calculations of the IR absorption spectrum of HOD also requires a spectroscopic map for the magnitude of transition dipole moment, 0 , for the
OD stretch relative to its value in the gas phase, 0g ,
0
= 0.71116 + 75.591 Eef f
0g
(5.4)
It is important to emphasize that the spectroscopic maps given by Eqs. (5.3) and
(5.4) were developed in the context of aqueous alkali halide salt solutions, and not
specifically for water in ILs. Comparisons of the results for the IR absorption spectrum and the FFCF for isolated HOD in [bmim][PF6 ] directly with experiment will
79
both provide validation and reveal the extent to which the spectroscopic maps are
transferable.
D
E
Rt
dteit
~ (t)
~ (0)ei 0 d ( ) et/2T1 ,
(5.5)
where h i represents a classical ensemble average, (t) = (t) hi is the fluctuation of the frequency from its average value, hi, and
~ (t) is the transition dipole
moment vector,
(5.6)
x10
A
cm1
OD .
(5.7)
The FFA expression, Eq. (5.5), approximately captures the effects of inhomogeneous broadening, motional narrowing, rotational broadening, and non-Condon transition dipole moments on the vibrational line shape. The effects of lifetime broaden
ing are captured empirically via the exp(t 2T1 ) factor, where T1 is the vibrational
population lifetime, 1.8 ps for the OD stretch of HOD in water.[193] T1 has not
been determined for HOD in [bmim][PF6 ]. For the calculation of the IR absorption
80
C (t) =
h(t)(0)i
.
C (0)
(5.8)
81
from which the frequencies are computed is naturally a sum of contributions from the
anions and cations, Eq. (5.3). Note that, for isolated water in an IL, the contribution
to the effective electric field from other water molecules can be ignored. Fortuitously,
the normalized time correlation function of the electric field fluctuations,
CE (t) =
hE(t)E(0)i
,
CE (0)
(5.9)
where E(t) = Eef f hEef f i is the fluctuation of the effective electric field from its
average value, is an excellent surrogate for C (t) . For a linear relationship between
the electric field and the vibrational frequency, the two normalized correlation functions are identical. For a quadratic relationship between the field and the frequency,
the functions can differ. However, for HOD in [bmim][PF6 ] the normalized correlation functions are almost quantitatively identical (vide infra). Thus, we will proceed
to decompose CE (t) and assume that the qualitative insights are relevant for C (t) .
Since E(t) can be expressed as a linear sum, Eq. (5.3), CE (t) can be decomposed
into contributions from anions and cations using the same approach that has proven
successful in unraveling the factors that influence solvation response functions in
ILs,[90, 171] proteins,[132] and DNA,[123126, 194]
CE (t) =
X C (t) X hE (t)E(0)i
E
=
,
CE (0)
CE (0)
(5.10)
where represents the solvent component of interest. This method of decomposing, CE (t), and C (t) by proxy, is rigorously consistent with the linear response
approximation, and has not previously been applied in the context of understanding
vibrational spectral diffusion in multicomponent liquids.
Each of the solvent component correlation functions, CE (t), in Eq. (5.10) can also
be further separated into contributions that arise from their respective translational
and rotational motions. The translational contribution to E , E ,trans , is calculated
82
by regarding each relevant IL molecule as a single point charge located at its center
of charge. The rovibrational contribution to E is then just the difference E ,rovib =
E E ,trans . These definitions allow the solvent component correlation functions
for the cations and anions to be decomposed into their respective translational and
rovibrational contributions,
(5.11)
where the functions CE,trans (t) and CE,rovib (t) are computed with Eq. (5.10), but
with E ,trans (t) and E ,rovib (t) in place of E (t).
83
increase of our statistics. The MD simulations were performed using the Largescale Atomic/Molecular Massively Parallel Simulator (LAMMPS) program.[134] All
molecules were modeled as fully flexible, except for covalent bonds containing hydrogen or deuterium which were fixed at equilibrium lengths using the SHAKE
algorithm.[135, 196] For the [bmim] molecules force-field parameters for the bonds,
bends, dihedrals, and atomic-centered Lennard-Jones sites were adopted from the
generalized Amber force field (GAFF).[136] Minor dihedral angle modifications were
made to better match density functional theory calculations carried out with a B3LYP
functional and the aug-cc-pVDZ basis set. Parameters for [PF6 ] are not available in
the GAFF and were obtained from Liu et al.[137] Atomic-centered partial charges
for the IL molecules were calculated via the Merz-Singh-Kollman[138] analysis of the
electron density of the optimized geometry of the molecules obtained with DFT with
a B3LYP functional and the aug-cc-pVDZ basis set. In an attempt to more accurately
model the dynamics of the system, the partial charges were empirically scaled by a
factor of 0.84, as suggested by DFT calculations for a similar IL, [bmim][BF4 ].[142]
Treating the charge scaling factor as a tunable force field parameter to approximately
describe the effects of electronic polarizability is commonly used as a means to more
accurately capture diffusion in ILs.[143] The long-ranged electrostatic interactions
in the simulations were computed with the particle-mesh Ewald summation method
with a 15
A real-space cutoff.[94, 139]
Out of concern for the long relaxation dynamics, we rely on a rigorous equilibration procedure identical to our previous work simulating ILs. In brief, the molecules
are allowed to relax during a minimization procedure after which the temperature
is slowly raised from 0 K to 300 K and maintained at 300 K for 4 ns in the NPT
ensemble controlled by a Nose-Hoover thermostat and barostat.[140] The size of the
simulation box was isotropically scaled to reflect the average density and was then
simulated in the NVT ensemble for 1 ns at 300 K, the temperature was slowly raised
84
to 600 K over 1 ns to destroy any pseudo-stable ionic cages that may have formed.
Next, the temperature was reduced back to 300 K in 1 ns, followed by an NVT simulation for 1 ns at constant temperature of 300 K. The final velocities were scaled to
300 K and a pre-production NVE simulation was performed for 11 ns. A total of 50
ns of continuous dynamics for the D2 O:IL system and 5 ns for the neat H2 O systems
were collected in the NVE ensemble with a 2 fs integration time step and a collection
resolution of 4 fs.
As a preliminary validation of the simulations and force-fields, we calculated the
orientational time correlation function for an OD bond in neat H2 O and in the
[bmim][PF6 ] IL, given as hP2 (
rOD (0) rOD (t))i, where P2 (x) is the second-order Legendre polynomial (Figure 5.1). The oscillations below 1 ps are indicative of water
librational motion and will be discussed in more detail in Subsection 5.3.1. The reorientational dynamics are clearly much faster in H2 O than in the IL. Experimental
measurements of the OD anisotropy decay in [bmim][PF6 ] were collected out to 40
ps, and a biexponential fit revealed two time constants: 2.4 and 24.7 ps.[116] The calculated rotational correlation function was fit to a tri-exponential function for t 1
ps (Figure 5.1). The three time constants were 3.5 ps, 19.4 ps, and 85.6 ps. The
first two time constants agree fairly well with experiment and serve as a validation
of the simulations. The longer time decay (85.6 ps) would not be resolvable in the
experiment because of the population lifetime of the OD vibrational reporter.
Rotational Correlation
IL
H2O
0.1
0.01
0.1
t (ps)
10
100
86
Figure 5.2. Vibrational line shapes for the OD stretch of dilute HOD in
H2 O and in the [bmim][PF6 ] IL. The spectra were arbitrarily scaled to have
the same maximum intensity.
87
TABLE 5.1
IR ABSORPTION DATA
HOD in H2 O
HOD in [bmim][PF6 ]
max (cm1 )
FWHM (cm1 )
Theory
2548
148
Expa
2510
170
Theory
2712
20
Expa
2678
21
Ref. [116]. Summary of the theoretical and experimental IR absorption line shapes for
the OD stretch of HOD in H2 O and in [bmim][PF6 ]. max is the frequency of maximum
absorption and FWHM is the full-width at half the maximum absorption.
164 cm1 (Table 5.1). Experimentally, the spectrum shifts by 168 cm1 and narrows
by 149 cm1 . The agreement between theory and experiment for the differences
in the line shapes between the aqueous and IL environments are excellent, which
validates both the simulations and the spectroscopic maps. Consistent with previous
studies[112, 113, 115] the peak of the OD stretch spectrum of HOD in water is to the
blue of experiment and the spectrum is slightly too narrow. In the IL the peak in the
spectrum is again to the blue of experiment, but its width is almost exactly correct.
As discussed previously, there is some ambiguity about the vibrational lifetime of
HOD in the IL, and the spectrum in Figure 5.2 assumes T1 = 1.8 ps, the same value
as HOD in H2 O. However, the lifetime is likely longer because the HOD molecule is
not hydrogen bonding and the 2D IR spectrum were collected out to 40 ps implying a
T1 longer than 1.8 ps. Therefore, the 20 cm1 width of the spectrum can be regarded
as an upper-bound. Taking T1 = provides a lower bound of 16 cm1 . The
significant narrowing of the spectrum in the IL solvent relative to aqueous solution
88
89
F(E)
IL
Cation
Anion
H2O
-0.02
0.02
0.04
E (au)
0.06
0.08
Figure 5.3. Distribution functions, F (E), for the projection of the electric
field projected along the OD of HOD in H2 O (black) and in the
[bmim][PF6 ] IL (turquoise). The distribution of electric fields in the IL
resulting from cations (blue) and anions (red) are also shown. The
distribution functions have all been scaled to have the same value at their
maximum.
90
91
time and a factor of two for the longest, 38 ps timescale. For HOD in water it has
been established that spectral diffusion occurs too quickly in non-polarizable water
models, by about a factor of approximately 1.52.[200] It is therefore likely that quantitatively reproducing the spectral diffusion timescales for HOD isolated in ILs would
also require electronically polarizable force fields. Nonetheless, the qualitative agreement between experiment and theory is reasonable enough to proceed to decompose
CE (t) for HOD in the IL to achieve additional physical insight. Already, the simple
absence of nanosecond timescales in both simulation and experiment demonstrate
that the OD vibrational reporter is insensitive to longer-time rearrangements that
have been observed in both theoretical and experimental investigations of solvation
dynamics in [bmim][PF6 ].[2, 79, 88, 90, 201, 202]
Before progressing to decompositions of CE (t) for HOD in the IL, it is important
to discuss the sub-picosecond damped oscillation that is evident in the electric field
correlation function for both HOD in water and HOD in the IL. Such oscillations
have been experimentally verified for spectral diffusion of HOD in liquid water and
assigned to a oscillatory stretching motion of the hydrogen bond between the OD
vibrational reporter and a neighboring water molecule.[203] The peak in the oscillation occurs at 120 fs for HOD in water, but at 280 fs for HOD in [bmim][PF6 ].
Also, the oscillation is considerably more pronounced in the IL. The decompositions
discussed below will reveal that the oscillation is related to translational motion of
the water relative to the anions. Thus, the physical interpretation is similar in the IL,
only now it is an oscillatory stretch within a [PF6 ] HOD [PF6 ] complex. Experimentally, significant oscillations were observed for the spectral diffusion of D2 O
in the [bmim][PF6 ] IL having a period of 0.3 ps. However, these oscillations were
assigned as quantum mechanical coherence oscillations due to anharmonic coupling
between the symmetric and asymmetric stretches of D2 O (i.e. the same oscillations
were observed in the center-line-slope of the diagonal and cross peaks of the symmet-
93
94
1
IL
Cation
Anion
0.8
C(t)
0.6
0.4
0.2
0
0.01
0.1
1
t (ps)
10
100
95
1
IL
Cation-Trans
Cation-Rovib
Anion-Trans
Anion-Rovib
0.8
C(t)
0.6
0.4
0.2
0
-0.2
0.01
0.1
1
t (ps)
10
100
96
97
CHAPTER 6
MONITORING INTRAMOLECULAR PROTON TRANSFER WITH
TWO-DIMENSIONAL INFRARED SPECTROSCOPY
6.1 Introduction
Proton transfer (PT) plays a critical role in many chemical, photochemical, catalytic, and biomolecular processes.[204, 205] It remains an important challenge to
elucidate the factors that affect the kinetic rates and mechanisms of PT in realistic
contexts. Novel spectroscopic approaches for monitoring PT processes in real time
are therefore essential. Because of its sub-picosecond time resolution and superb
sensitivity of infrared reporters to their local environments, chemical exchange twodimensional infrared (2D IR) spectroscopy[206, 207] has the ability to offer tremendous insight regarding the dynamics of thermally activated PT. Chemical exchange
2D IR spectroscopy requires a suitable IR active mode whose vibrational frequency is
sensitive, i.e. strongly coupled, to the PT reaction coordinate. A potential strategy
is to monitor directly the bonds in which the transferring proton participates. While
such an approach is necessarily completely non-perturbative, a likely drawback is the
complexity of the resulting spectra because of tunneling and nonadiabatic effects.[208]
An alternative approach is to introduce a spectroscopic reporter whose vibrational
frequency is sensitive to the PT process, but whose presence is minimally perturbative
to the motion (e.g. mechanism and kinetics) of the transferring proton of interest.
Selective deuteration of carbon atoms in the vicinity of the PT event can potentially
offer a means to monitor the reaction with minimal perturbation. Site-specific C-D
98
bonds generally absorb between 2100-2300 cm1 , a region of the IR spectrum that
is mostly absent of other vibrational transitions in biomolecular contexts, and are
known to be excellent reporters of their chemical environment.[209, 210] Moreover,
since carbon is rarely the donor or acceptor in most PT processes of interest, C-D
vibrations will be adiabatically decoupled from the PT reaction.
The use of CD to monitor the kinetics of PT processes using chemical exchange
2D IR spectroscopy was demonstrated and analyzed computationally for the model
compound malonaldehyde (3-hydroxy-2-propenal, Figure 6.1). Malonaldehyde contains an intramolecular hydrogen bond across which a proton can transfer between
symmetric donor and acceptor oxygen atoms (OA H OB ), a process that has been
studied extensively by both theory[211214] and experiment.[215218] In this study,
one of the carbonyl/enol carbon atoms, a direct neighbor to the proton transfer event,
is deuterated. This particular CD vibrational reporter is likely to be exquisitely
sensitive to the PT event because of (1) its spatial proximity, (2) the known sensitivity of CD vibrational frequencies to the movement of charge via the vibrational
Stark effect,[219] and, most importantly, (3) the coupling of the CD bond to the
dramatic change in the electronic structure of the malonaldehyde molecule upon
99
intramolecular PT. The chemical environment of the carbon-atom to which the deuterium probe is attached changes markedly from HOA CD=C to OA =CDC when
the proton transfers. In essence, this change in the electronic structure of the malonaldehyde molecule results in a substantial alteration of the force constant of the CD
bond. In the gas phase, density functional theory (DFT) at the B3LYP/6-311+G(d,
p) level of theory/basis set predicts a 179 cm1 shift in the harmonic vibrational
frequency of CD vibrational probe. This large shift contrasts significantly with the
< 10 cm1 shifts observed due to the vibrational Stark effect in previous experimental studies,[209, 210, 219] which provides a qualitative indication of the importance
of the electronic structure change to the CD vibrational frequency as well as an
important experimental design principle. Classically, labeling the carbonyl/enol carbon atoms in malonaldehyde with a deuterium should have a negligible effect on the
kinetic rate of intramolecular PT because the free energy profile for the PT process
will be unchanged and there is more than a 1000 cm1 mismatch between the O-H
and CD vibrational frequencies. Quantum mechanically, however, there could be an
indirect effect due to altering the zero-point-energy of the proton on the labeled side
of the molecule relative to the unlabeled side of the molecule. Also, nonadiabatic
coupling of nuclear motions to the electronic structure of the molecule could be relevant. These potentially interesting quantum mechanical effects will be ignored for
the purposes of the present proof-of-concept study.
6.2 Methodology
2D IR spectroscopy has been utilized to investigate complexation reactions in
solution,[206, 207, 220] including hydrogen-bond formation and dissociation processes. In particular, Nydegger, Rock, and Cheatum have used 2D IR spectroscopy to
investigate CD labeled formic acid dimmer in hexane solution.[220] Unfortunately,
the interpretation of the spectra was complicated by the presence of an accidental
100
Fermi resonance so the kinetics of the intermolecular double PT process could not
be elucidated. The technique requires that the reactant (A) and product (B) species
have well-defined spectral signatures. At zero waiting time, peaks appear along the
diagonal that correspond to A and B. As the waiting time is increased, off-diagonal
peaks appear that correspond to the formation of A from B and B from A. Kinetic
rate constants for both the forward and back reactions, as well as the equilibrium
constant between A and B can then be extracted from the growth of the off-diagonal
peaks and the decay of the diagonal peaks (the effects of vibrational population relaxation must also be taken into account). In this study, the 2D IR spectra of CD
labeled malonaldehyde in aqueous solution will be calculated to demonstrate how
the technique is applicable to the study of thermally-induced PT reactions. Because
the intramolecular PT reaction is symmetric in malonaldehyde, the resulting 2D IR
spectra will be symmetric and the diagonal peaks should decay at the same rate as
the off-diagonal peaks grow (neglecting vibrational population relaxation).
In order to calculate the 2D IR spectrum of CD labeled malonaldehyde it is first
necessary to map the instantaneous CD vibrational frequency to the PT reaction
coordinate,
R(OA H) cos(OB OA H)
R(OA OB )
(6.1)
where R(OA H) is the distance from the transferring proton to the donor oxygen
atom, R(OA OB ) is the distance between the donor and acceptor oxygen atoms, and
(OB OA H) is the angle between the OA H and OA OB bonds (see Figure 6.1). The
transition state for the intramolecular PT is located at a value of = 0.5. Using DFT
with the B3LYP functional and a 6-311+G(d, p) basis set, optimized geometries of
malonaldehyde in the gas-phase were obtained for 40 values of constrained between
0.1 and 0.9. All gas-phase electronic structure calculations were performed in Gaussian 09.[221] The energies of the optimized geometries are plotted in the top panel
101
Figure 6.2. (top) Potential energy curves for the intramolecular proton
transfer in malonaldehyde generated with DFT and SCCDFTB. The DFT
barrier height is 3.2 kcal/mol while SCCDFTB predicts a barrier of 2.6
kcal/mol. (middle) Free energy profile from a QM/MM simulation of
malonaldehyde in water with a barrier height of 4.1 kcal/mol. (bottom)
Anharmonic CD vibrational frequencies as a function of the proton
transfer reaction coordinate for malonaldehyde in the gas-phase. The
frequencies were fit to Eq. 6.2, where A0 = 1534.0, A1 = 91.5, A2 = 11.8,
A3 = 2106.5, A4 = 42.7, and A5 = 7.0.
102
of Figure 6.2. DFT predicts a barrier to PT of 3.2 kcal/mol, which agrees well with
higher level quantum chemistry calculations (e.g., MP2/cc-pVTZ and CCSD(T)/ccpVDZ predict barriers of 2.8 and 3.9 kcal/mol, respectively).[222, 223] For each of
the geometries (i.e. values of ), the anharmonic CD vibrational frequency of interest was calculated using previous methodology.[224227] Briefly, the CD bond is
stretched from 0.88 to 1.44
A in 0.08
A increments, holding the rest of the molecule
fixed. At each increment, the molecular energy is calculated with B3LYP/6-311+G(d,
p) yielding the Born-Oppenheimer potential energy curve for the CD stretch, which
is fit to a Morse oscillator. The Morse parameters are sufficient to determine the 01
vibrational frequency, since the energy levels are known analytically for a Morse oscillator. The CD vibrational frequencies are shown as a function of in the bottom
panel of Figure 6.2. Note the extraordinary sensitivity of the CD stretch to the PT
reaction coordinate. The mapping of the CD stretch frequency to is completed by
utilizing an appropriately flexible fitting function,
(6.2)
mized with DFT were utilized for the SCCDFTB energy calculations. The DFT
and SCCDFTB potential energy curves are qualitatively similar. The two primary
differences are in the barrier region (SCCDFTB predicts a 1.5 kcal/mol lower barrier
than DFT) and in the repulsive parts of the potential.
The SCCDFTB-based QM/MM molecular dynamics (MD) simulations of malonaldehyde solvated by 2932 water molecules were performed in AMBER 10.[231]
The simulations employed periodic boundary conditions with a cubic simulation box,
and the long-ranged electrostatic interactions were treated with the particle mesh
Ewald (PME) method.[139] The SHAKE[196] algorithm was used to constrain the
geometry of the rigid SPC/E water molecules. Our equilibration protocol involved
(1) 500 steps of steepest descent minimization, (2) 500 steps of conjugate gradient
minimization, (3) a gradual defrost from 0 K to 300 K over 200 ps of simulation in
the NVT ensemble with a Langevin thermostat and a 1 fs time step, (4) 200 ps of
simulation in the NPT ensemble, (5) rescaling the simulation box size to the average
of the last 50 ps of the NPT simulation (45
A), (6) 100 ps of NVT simulation,
(7) rescaling the velocities to 300 K, and (8) 100 ps of NVE simulation. A 105 ns
trajectory in the NVE ensemble was then collected for analysis.
For each snapshot in the production run trajectory, the instantaneous value of
the PT reaction coordinate, Eq. (6.1), was calculated. A histogram of (t) was
constructed, P (), from which the free energy, F , of the intramolecular PT reaction
in malonaldehyde could be calculated using the relationship F = kB T ln(P ) (middle
panel of Figure 6.2). The free energy barrier height for the PT reaction in aqueous
solution in solution was 4.3 kcal/mol, which is in excellent agreement with a previous
SCCDFTB simulation of malonaldehyde in water (4.2 kcal/mol).[232] From the
time dependence of , a trajectory of the CD stretch vibrational frequency, (t),
was constructed via the relationship in Eq. (6.2).
As described in Chapter 1, knowledge of (t) is sufficient to calculate linear IR
104
105
(6.4)
t1 +t2
where RRP and RN P are the rephasing and non-rephasing responses, respectively.
The waiting time, Tw , is synonymous with t2 in the equations above. The 2D IR
signal S(3 , t2 , 1 ) is given by the sum of the rephasing and non-rephasing signals,
106
S(3 , t2 , 1 ) Re [SRP (3 , t2 , 1 ) + SN P (3 , t2 , 1 )]
(6.5)
where
Z
SRP (3 , t2 , 1 ) =
dt1
Z0
Z0
dt3 exp(i3 t3 + i1 t1 )RN P (t3 , t2 , t1 )
dt1
SN P (3 , t2 , 1 ) =
0
(6.6)
where SRP and SN P are the rephasing and non-rephasing signals, respectively.
108
Figure 6.4. (top) Reaction coordinate time correlation function along with
a fit to a single exponential with a time constant of 28.8 ps. (bottom)
Evolution of the normalized volumes of the diagonal and off-diagonal peaks
in the 2D IR spectra as a function of the waiting time. Both curves were fit
to a single exponential yielding time constants of 29.7 and 28.3 ps for the
diagonal and off-diagonal peaks, respectively.
109
CHAPTER 7
SUMMARY
interactions in ILs that are responsible for microscopic structures and dynamics that
ultimately manifest in macroscopic physical properties.
In Chapters 2 and 3, we identified the persistence of preferential solvation, where
the cations are, on average, closer to the the aromatic solute than the anions. While
presenting some ambiguity in the interpretation of simulations and experiments that
depend on a spectroscopic probe to be a passive observer of the local environment,
scientists and engineers can utilize this knowledge to selectively tune solubility of
compounds by choosing the right combination of cation and anion constituents.
The mechanism of solvation in ILs is distinctly different from conventional dipolar
solvents, where collective dipole-dipole interactions in the vicinity of the fluorescence
probe molecule are the most dominant interaction. In ILs, the media is no longer
a single component liquid, rather a heterogeneous mixture, and because of their
different shapes, sizes, and charge distributions the ions respond differently to the
charge perturbation. However, extensive MD simulations in a series of imidazoliumbased ILs, [emim][BF4 ], [bmim][BF4 ], [bmim][DCA], [emim][TfO], and [bmim][PF6 ]
revealed a general solvation dynamics mechanism despite these differences in ions.
Consistently, the translational motion of the anions into and out of the first solvation
shell of C153 are most responsible for the solvation response. While initially this
mechanism appears distinct from polar solvents, if considering particular cation-anion
pairs form a molecule with a fictitious dipole moment, it is the rotation of these
fictitious molecules that dominate the response (Figure 7.1). The concept of the
fictitious dipole molecule is a proof-of-concept, with the current definition identifying
any anions with 7.75
A of the center-of-mass of the cations. The distance 7.75
A was
identified as the first minimum in the radial distribution function of the center-ofmass of the cations relative to the center-of-mass of the anions.
Analogous to experimental observations that the solvation relaxation is correlated
with viscosity (Chapter 1), a comparable resemblance is found when relating the
111
112
113
theoretical solvation time to the inverse of the cube root of the molecular volume
(Figure 7.2). Predicting relevant solvation time scales is beyond the scope of this
study, though a survey of additional ILs would be beneficial.
One of the most daunting scientific challenges facing our society today is the
production of environmentally clean and renewable energy. Chemists and engineers
are no longer dependent on varying the reaction conditions as a means for control over
rates and products; now selectivity over the reaction media represents a paradigm
shift in our approach to chemical reactions in the condensed phase. This research
which characterized the structure and dynamics in ILs in unprecedented detail, will
benefit other scientists and engineers who are seeking to control the properties of ILs
for advanced applications in energy research.
115
Cations
Anions
[bmim]
[BF4]
[Tmet]
[emim]
[Triazo]
[Tf2N]
[Pyrazo]
[S222]
[TfO]
Figure 7.3. The optimized structures of cations and anions. The cations are
1-butyl-3-methyl imidazolium, [bmim], 1-ethyl-3-methyl imidazolium,
[emim], triethyl sulfonium, [S222 ], and tri(methoxymethyl)-methyl
phosphonium, and [Tmet]. The anions are tetrafluoroborate, [BF4 ],
trifluoro-methane sulfonate, [TfO], 1-pyrazolide, [Pyrazo], 1,2,3,-triazolium,
[Triazo], and bistrifluoromethylsulfonylimide, [Tf2 N]
116
117
118
119
120
121
122
123
APPENDIX A
SOLVATION RESPONSE FUNCTION FITS
124
Figure A.1. Fits of the calculated (black) and experimental (red) solvation
responses of C153 in the IL [emim][BF4] to a single exponential function in
the time range between 50 ps and 400 ns. The data are shown as filled
circles, while the fits are lines.
125
Figure A.2. Fits of the calculated (black) and experimental (red) solvation
responses of C153 in the IL [emim][BF4] to a single exponential function in
the time range between 50 ps and 400 ns. The data are shown as filled
circles, while the fits are lines.
126
Figure A.3. Fits of the calculated (black) and experimental (red) solvation
responses of C153 in the IL [emim][BF4] to a single exponential function in
the time range between 50 ps and 400 ns. The data are shown as filled
circles, while the fits are lines.
127
Figure A.4. Fits of the calculated (black) and experimental (red) solvation
responses of C153 in the IL [emim][BF4] to a single exponential function in
the time range between 50 ps and 400 ns. The data are shown as filled
circles, while the fits are lines.
128
Figure A.5. Fits of the calculated (black) and experimental (red) solvation
responses of C153 in the IL [emim][BF4] to a single exponential function in
the time range between 50 ps and 400 ns. The data are shown as filled
circles, while the fits are lines.
129
TABLE A.1
IDEAL MULTIPLICATIVE CONSTANTS
RMSD (102 )
[emim][BF4 ]
1.17
3.9
[bmim][BF4 ]
0.78
3.2
[bmim][DCA]
0.945
2.7
[emim][TfO]
0.79
6.1
[bmim][PF6 ]
0.71
8.0
Ideal multiplicative constants, k, for experimental solvation response data that minimized the root-mean-square deviation (RMSD) for each IL system.
130
APPENDIX B
MALONALDEHYDE TWO-DIMENSIONAL INFRARED SPECTRA
Shown in this appendix are chemical exchange two-dimensional infrared (2D IR)
spectra for the CD stretch of labeled malonaldehyde in aqueous solution for waiting
times, Tw in the range 0 to 500 ps referred to in Chapter 6.
131
132
133
134
135
136
137
138
139
140
141
Figure B.11. Chemical exchange 2D IR spectra for waiting times of 100 ps.
142
Figure B.12. Chemical exchange 2D IR spectra for waiting times of 200 ps.
143
Figure B.13. Chemical exchange 2D IR spectra for waiting times of 500 ps.
144
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