AFOSR

MOLECULAR DYNAMICS &

THEORETICAL CHEMISTRY
17 March 2011
MICHAEL R. BERMAN
Program Manager
AFOSR/RSA
Air Force Office of Scientific Research
Distribution A: Approved for public release; distribution is unlimited. 88ABW-2011-0801
 2011 AFOSR SPRING REVIEW
2303E PORTFOLIO OVERVIEW
NAME: Michael Berman

BRIEF DESCRIPTION OF PORTFOLIO:

Research on understanding and exploiting chemical reactivity and
energy flow in molecules to improve Air Force systems, processes,
and materials.

Understanding and exploiting chemical reactivity and catalysis for

improved storage and utilization of energy

LIST SUB-AREAS IN PORTFOLIO:

Molecular Dynamics
Theoretical Chemistry

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 Challenges in Chemical Dynamics
Molecular Dynamics, Theoretical Chemistry, Nanoenergetics

• Energetic Materials (Rocket propellants, explosives)

– Energetic ionic liquids  CHNO limit; new approaches
– Energetic nanostructures  Sensitivity, mechanisms
– Non-traditional concepts  Safer, penetrating munitions

• Atm/Space Chemistry (Signatures, surveillance)

– Upper atmosphere, space  Hypersonic prop, gas/surf interact.
– Signatures & backgrounds  Rates/mech. of ion-molecule proc’s.
– Ion & plasma processes  Predictive codes, communication

• Nanostructures/Sensors (Catalysis, Sensing)

– Nanostructures for catalysis  Atomic scale imaging and control
– Surface-enhanced detection  Size-dependent properties

• Lasers and Diagnostics (Infrared lasers, missile defense)

– High-Power Gas Lasers  Efficient pumping, energy transfer
– Novel analytical tools/methods  Relaxation processes
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 Scientific Challenges

• Control and Imaging of Catalysis

– Understanding of mechanisms – new dimensions in catalysis
– Bringing together new developments in ability to:
• Prepare
• Probe
• Predict
the properties, reactions, and interactions of nanostructures
– Makes prohibitively slow processes practical
• Catalysis is key to energy storage and fuel production
• Important practical military and industrial impacts
• Co-catalysts, promoters, substrates, new materials, …
• Plasmonics
– Exploit high local E fields; novel sensing
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 Transformational Opportunities

• Secure, sustainable energy supply

CO2 JP8

• Endothermic Fuels for cooling high-speed vehicles

– Mission enabled by catalysis

• Dual mode propellants for satellites

– Ionic liquids for main thrusters and station keeping

5
 Research Environment: Other Orgs.
That Fund Related Work

• NSF – Covers all areas of chemistry

– Center on Powering the Planet (water splitting)

• DoE – Basic Energy Sciences

– Hub on Solar Fuels
• From research to industrial production
• Transition mechanism
• Congressional line item
• AFOSR research funds fundamental, underpinning
work on understanding catalytic mechanisms
– Use tools of physical chemistry to probe catalytic mechanisms
– Active sites, size-selected clusters, role of local environment
– Ways to control catalysis: mixed metals, substitutes for rare mat’ls
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 Program Trends

• Catalysis
• Sustainable Energy
• Small Molecule Activation

• Ionic Liquid Propellants

• Plasma / Ion Chemistry/Interfaces

• Hybrid Chemical Lasers

• Sensors for Trace Detection
• Modeling of Material Properties

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 Recent Transitions

• Al-cluster based energetics

(Bowen, Johns Hopkins; Castleman, Penn St.)
– Funding from DTRA, ONR
– NSWC, Indian Head (Jim Lightstone)
– First materials produced in apparatus

• Atomic Layer Deposition / Molecular Layer Deposition

(George, Colorado)
− ALD gas diffusion barrier technology is being
developed actively by DuPont
− ALD on polymers of Copper-Indium-Gallium-Selenide
(CIGS) for flexible solar photovoltaic cells
− ALD of Al2O3 best deposition method for pinhole and
defect free coatings – prevents O2/H2O penetration
(Al2O3 ALD coating of 10 nm provides barrier equal to glass)
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 Carbon-Neutral Fuels: Converting
Carbon Dioxide to Fuels
Objective: Approach:
• Produce energy dense hydrocarbons • Develop new electrocatalysts to
and alcohols using CO2 as a feedstock efficiently produce alcohols and
carbon-carbon bonded products from
CO2 and sunlight feedstocks
Blue light (465
nm) is used to • Identify key mechanisms and
convert CO2 to dynamics related to the necessary
alcohols with a multielectron processes.
substituted
pyradine catalyst Payoff:
and a p-GaP • A secure and sustainable source
electrode
of liquid fuels for aircraft use
• A carbon neutral fuel – CO2
produced in combustion is offset
Key intermediate in pyridinium
catalysis of CO2 reduction by using CO2 as a feedstock

Solar fuels store the energy from the sun in energy- Prof. A. Bocarsly
dense chemical bonds for use as transportation fuel. 9
 Isolation of Key Intermediate in
CO2 Reduction Process
• Photoelectrochemical conversion of CO2 to fuels using pyridine as a catalyst
− Isolation of key carbamate radical anion intermediate in a supersonic expansion by
reaction of pyridine and (CO2)n‾ clusters
− IR spectra confirms proposed mechanism involving the formation of a covalent
bond between CO2 and pyridine

• Transfer rxn components from New C-N covalent

solution to the gas phase using bond formation

non-destructive ionization methods

• Exploit recent advances in
Prediss. Yield

cryogenic ion chemistry to quench

reaction intermediates into cold,
stable complexes
• Structurally characterized with high 1000 1200 1400 1600 1800 2000 2200 2400
resolution infrared spectroscopy
Photon Energy, cm-1

Johnson and co-workers, Yale University

JACS Communication, 132, 15508 2010.
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 New Electrocatalytic Process for
CO2 Reduction Observed by SHG

• Wasted energy in CO2 reduction

Potential cycles
from 0.5 to -1.4 V
vs SHE show
gradual buildup of
CO on surface
due to large overpotential
• Room-Temperature Ionic Liquid
(RTIL) forms stable complex with
CO2- on Pt surface and reversibly
catalyzes CO2 to CO conversion
• Process observed with compact
broadband SFG spectrometer
utilizing femtosecond IR pulses to
obtain spectra at electrode-
electrolyte interfaces
Dlott, Masel, U Illinois Urbana-Champaign11
Plasmon-Resonant Enhancement of
Photocatalytic Water Splitting
• Photodriven splitting of water to
H2 and O2 on TiO2 substrates is
greatly enhanced (x66) by the
presence of Au nanoparticles.
• Use highly catalytic TiO 2 with
highly plasmonically active Au
nanoparticles
• Local E-field enhancement near
the TiO2 surface increases
electron-hole pair generation at
the surface of the TiO2
• Larger enhancement factors
possible if this mechanism can
be optimized.

Cronin, U Southern California

Nanoletters, 2011 12
Fuel Cooling Technologies Enable Hypersonic Systems
(from UTRC)
New fuel-cooling technologies will increase reliability of hypersonic demonstrators, and are
required for longer duration, higher Mach number hypersonic vision vehicles.

160
Flight Duration - minutes

Long-Range Strike
coke tolerance requirement

120 (e,g, Falcon) Access

Existing to Space
Technologies
New Technologies
Required High
80
Speed
X-51
Missile
Scramjet
Demo
40

TBCC
Demo
0
0 2 4 6 8 10
Mach Number

fuel heat sink requirement

Next Generation Endothermic Fuels Technology 13
 Endothermic Fuel Cooling Challenges (from UTRC)

Section of Combustor Wall HEX

Cooling Channel in HEX
Fuel Heat in from Coke Deposit Heat
in combustor
Fuel
Exit Fuel Fuel

Heat Exchanger Wall

Endothermic Technology Goals:

Initiate Cracking
Earlier & Increase 

Heat Sink, BTU / lbm

Endotherm Increase Coking Limit

Wall Heat Load
DH = Qwall / Wfuel
 (~2 hr. run duration)

Tfuel Twall
Limit Material
Limit

Fuel Exit Temperature

Next Generation Endothermic Fuels Technology 14
 Cyclohexane Dehydrogenation:
Cluster Size Affects Selectivity
Untreated MWNT HNO3 Treated MWT, Annealed
Large Pt Clusters ( 2.15 nm) Small Pt Clusters ( 1.32 nm)

TOR (molecules / Pt atom/ s

1.0 1.0
Pt MWNT
TOR (molecules / Pt atom/ s

0.9 Pt MWNT HNO3 hT

0.9 H2
o o
0.8 225 C 0.8 225 C
0.7 0.7
0.6 H2 0.6
0.5 C6H12 0.5 C6H12
0.4 C6H10 0.4
0.3 0.3
0.2 0.2 C6H6
C6H6 C6H10
0.1 0.1
0.0 0.0
UNTITLED
UNTITLED

Cyclohexene is predominant product. Benzene is predominant product.

Synthesis: Lisa Pfefferle, Gary Haller et al (Yale) 15
GISAXS exp’ts shows particles don’t change or sinter
 Cyclohexane Dehydrogenation:
Cluster Size Affects Selectivity
• Calculations with DFT/MP2, and Kinetic Monte
Carlo simulations of surface reactivity
• Smaller nanoparticles have a larger percentage of
step/edge sites; more reactive, stronger binding
• Binding energy of cyclohexene to the larger
particles is weaker than that on smaller particles

Desorption Pt55 Pt201

Dehydrog.

● Smaller Pt particles favor dehydrogenation to ● Larger Pt particles favor desorption of

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benzene. cyclohexene. Theory: Neurock, U Virginia
 Size-Dependent Binding Energies
Can Have a Big Impact on Catalysis

Volcano Decomposition
plot HCO2H (formic acid)

Pt55

1.32 nm

Pt201

2.15 nm
M – CO2H

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 Shape-Dependent Product
Formation over (Au)-FeOx
Temperature Programmed Surface Reaction
Pretreatment: 30 min. in 10% H2/He
4%O2/3840 ppm Cyclohexane/He,
Fe3O4
70 mL/min., 0.043 g.s/mL
1 300

Temperature (°C)
78 amu 44 amu CO2
•
RGA Signal (a.u.)

250 Cyclohexane dehydrogenation

▬▬ Octahedra 200
• Enhanced benzene production
▬▬ Cubes 150
for octahedra vs cubes
100

50
• Higher benzene selectivity for
0 gold-containing catalysts
Au-Fe3O4 • Good nanoparticle stability and
strong Au-O-Fe interaction
1 300
78 amu CO2 seem to favor cyclohexane

Temperature (°C)
44 amu
RGA Signal (a.u.)

250
dehydrogenation over oxidation
200
▬▬ Octahedra
150
▬▬ Cubes
100
50

0
500 1000 1500 2000 2500 500 1000 1500 2000 2500
Time (s)

M.B. Boucher, S. Goergen, N. Yi and M. Flytzani-Stephanopoulos, Phys. Chem. Chem. Phys. 18

18
 Catalytic Enhancement of Ignition
of Combustion
Pd-based multi-centered nano-ignitors via catalytic heat release

• Ignition of methane enhanced by in situ generated Pd nanoparticles

Shimizu et al. Combustion and Flame, 2010. (gas/surface model)
Van Devener et al. Journal of Physical Chemistry C, 2009
• Pd particles act as multi-centered nano-scale ignitors via catalytic heat release.
• Smaller particle size (1-5 nm) – weakened Pd-O bond strengths; Lower O2
desorption energy .
• Use support (TiO2, Al2O3 nps, etc.), other metals, to tune electron density 19
Wang, USC (MURI)
Temperature-Controlled Selectivity
in Catalytic Reactions of Methane

Landman, Ga Tech, Bernhardt, Ulm

Ang. Chem. Int’l Ed, 2010
20
J. Phys. Chem. C., 2011
 Temperature-Controlled Selectivity
in Catalytic Reactions of Methane
Ethylene production Methane combustion

T- selectivity High T Low T 21

 Graphene, Graphene Oxide, and
Clusters

• Graphene sheets oxidize from

the edges inward
• Oxygen clusters at defects sites
• Metal clusters can bind at
defect sites; distorts sheet

Fe13

Al13

Selloni, Car, Aksay, Princeton Univ.

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 Developing Theoretical Tools to
Apply to Catalysis
• 2010 Nobel Prize for “Pd-catalyzed
cross couplings”
• Previous: DFT with existing
functionals is qualitatively wrong for
coupling of an alkene to a Pt or Pd
center.
• Accomplishment: Developed new
hybrid functionals (M06) that are 10
qualitatively correct and allow DFT to
be applied to this important Nobel-
Prize-winning class of reactions.

“Binding Energy of d10 Transition Metals to Alkenes by

Wave Function Theory and Density Functional Theory,”
B. B. Averkiev, Y. Zhao, and Donald G. Truhlar,
Journal of Molecular Catalysis A 324, 80-88 (2010).
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Truhlar, U Minnesota
 Metal Hydride Functional Ionic
Liquid Fuels
 Remarkable impact of cation structure on reactivity noticed in higher performing
metal hydride-base anions - could be a novel design tool!
H Ignition
N N B
CN
responds 11
H
H [ms]
Me
H
Ignition
responds 600
N N B
H CN [ms]
H

 So far, all hypergolic ILs are based on known anions – efforts move to design of
unprecedented anions incorporating highly reactive hydrazine functionalities
IDEA: Novel hydrazino tetrazolate anions SUCCESS: Novel hydrazino tetrazole precursors prepared
N N N N
N N X-ray structure
N NHNH2 N NHNH2
N NHNH2
N N
n N 3
n
H H

 High energy density ILs for both electrospray and chemical propulsion- ‘Dual Mode’
propulsive capabilities being realized (Collaboration: with Yu-Hui Chiu/AFRL/RV)

Isp ~ 5000 s ( electrospray/ion only mode)

Isp >> Hydrazine (chemical mode)
• Stable electrospray emission High Isp for station keeping, rephasing & deorbit
High thrust for rapid response
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Hawkins, Schneider, AFRL/RZ
 Ionic Liquids Ignition
EMIM+NTf2- + NH4+
• First ion/pair-ion reactivity studies of vaporized EMIM+NTf2- NH4+
ILs using selected-ion flow tube reactor:
A + + X-B+  A+X-B+
(AFRL/RZ and A. Viggiano/AFRL/RV)

• First kinetics model to successfully describe ignition 2K

HNCO + HNO3
delay times and identify important reactions involved K
K = Rate
in IL ignition with WFNA 1/2K Constant
(AFRL/RZ and L. Catoire/thru EOARD) Products

• Identified new thermal decomposition pathways

for imidazolium based ILs – reactions may
compete with oxidation (AFRL/RZ and Leone D
Group/UC Berkeley)

25
 Discovered New Plasma Process:
e- Catalyzed Mutual Neutralization
• A+ + XY- + e-  neutrals + e-
3

–
2
Phys. Rev Lett. 106, 018302 (Jan. 2011)
Goodness of Fit

Poor fit without ECMN

• Never mentioned in literature
• Correlates with IR intensity
1
9
8
7 w/ ECMN
6

5
w/o ECMN
• Requires new mechanism
-8 4 5 6 7 8
involving motion-induced
3x10
3 -1
MN rate constant (cm s )
transitions
6 • Robust, several Br2- sources
Ar+ + XY- + e-  neutrals + e-
kECMN (x10-18 cm6 s-1)

5 yield the same result

4 • rate constants vary from 10-19
3 to 10-17 cm6 s-1
PSCl2- SF4- SF6-
2 PSCl-
POCl3- Impacts all negative ion plasmas
1 Br2- SF5- reentry
Cl2- -
plasma assisted combustion
0 POCl2- COCl2

0 500 1000 1500 2000 ……

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Low Frequency IR Intensity (km mol-1) Viggiano, AFRL/RV
 Summary

• Catalysis can have transformational impacts on DoD systems

• Catalysis greatly impacts energy storage and utilization
• New dimensions in catalysis research are emerging
• Knowledge of the molecular mechanism is key in developing
and optimizing more efficient catalysts
• AFOSR leading the way in applying new tools to understand
catalytic mechanisms
• Many new areas of opportunity:
− Bio-based fuel production
− Atomic scale imaging and control of catalysis

27