A Di D i S d f S E T f R fi d i h N l M dA Direct Dynamics Study of Super Energy Transfer Refined with Normal ModeA Direct Dynamics Study of Super Energy Transfer Refined with Normal ModeA Direct Dynamics Study of Super Energy Transfer Refined with Normal Mode y y p gyS liSamplingSamplingREPLACE THIS SamplingREPLACE THIS p g

j i k d h S i hBOX WITH YOUR Benjamin Datko and Jonathan SmithBOX WITH YOUR Benjamin Datko and Jonathan SmithORGANIZATION’S Benjamin Datko and Jonathan SmithORGANIZATION S

D t t f Ch i tHIGH RESOLUTION Department of ChemistryHIGH RESOLUTION Department of ChemistryLOGO p yLOGO

Temple UniversityTemple UniversityTemple University

INTRODUCTIONABSTRACT INTRODUCTIONABSTRACT Fi 2 (L ft) ill t t h t h d ’INTRODUCTIONABSTRACT Figure 2 (Left) illustrates hot hydrogen’s ABSTRACT g ( ) y gtrajectory as a function of two different anglestrajectory as a function of two different angles

ith t t b di id ’ t fCombustion of hydrocarbons results in a In order to get a better idea of the collisions a direct dynamics with respect to carbon dioxide’s center of mass. Combustion of hydrocarbons results in a In order to get a better idea of the collisions a direct dynamics pCosine sampling is used to introduce a biaswide range of energetic intermediates approach is taken Zhang and coworkers use electronic Cosine sampling is used to introduce a bias wide range of energetic intermediates approach is taken. Zhang and coworkers use electronic into the experimental parameters

including translationally hot hydrogen and structure methods to understand the reaction of HO+D2 HODinto the experimental parameters.

including translationally hot hydrogen and l i l d b di id (CO ) Thi

structure methods to understand the reaction of HO+D2 HOD D Th i h d h b id d i f i l B3LYP dultimately produces carbon dioxide (CO2). This + D. Their research used hybrid density functional B3LYP and Fi 3 (Ri ht) h th iti fultimately produces carbon dioxide (CO2). This

k t di t ti l lli i f h t D. Their research used hybrid density functional B3LYP and

H t F k th d [3] Di t d i kFigure 3 (Right) shows the position of

work studies computational collisions of hot Hartree-Fock method.[3] Direct dynamics makes no g ( g ) p

the Hydrogen’s trajectory stepwise Theo stud es co putat o a co s o s o oth d t ith b di id H

a ee oc e od [3] ec dy a cs a es oti b t th t ti l h f d th

the Hydrogen s trajectory stepwise. The hydrogen atoms with carbon dioxide. Here we assumptions about the potential energy hyper surface and thus colors of the markers indicatey guse direct dynamics where energy and forces

p p gy ypallows liberty of the hydrogen atom to interact with the target

colors of the markers indicate vibrational energy transferreduse direct dynamics where energy and forces allows liberty of the hydrogen atom to interact with the target vibrational energy transferred. y gy

are computed on the fly using quantumy y g g

molecule such as carbon dioxide (CO ) The hydrogen atom isare computed on the fly using quantum molecule such as carbon dioxide (CO2). The hydrogen atom is chemical calculations and this methodology given a mass weighted velocity As the hydrogen atom moveschemical calculations and this methodology given a mass weighted velocity. As the hydrogen atom moves does not assume the potential energy surface along the trajectory the forces are calculated and the resulteddoes not assume the potential energy surface along the trajectory, the forces are calculated and the resulted of CO2 at any time during the calculation. energy transfers are collected Molecular dynamics trajectoriesof CO2 at any time during the calculation. T j t i f h d t hi

energy transfers are collected. Molecular dynamics trajectories th b t d ith f d d t d “ thTrajectories of hydrogen atom approaching can thus be computed with forces and energy updated “on theTrajectories of hydrogen atom approaching

b di id B O h ican thus be computed with forces and energy updated on the fl ” d t i fitt d t ti l f [3]carbon dioxide use Born-Oppenheimer fly” as opposed to using fitted potential energy surfaces.[3]pp

molecular dynamics to model the interactiony pp g p gy [ ]

Using Born Oppenheimer Molecular Dynamics (BOMD) asmolecular dynamics to model the interaction. Using Born Oppenheimer Molecular Dynamics (BOMD) as yThis quasi classical approach allows us to

g pp y ( )the computational methodology is a reasonable approach TheThis quasi-classical approach allows us to the computational methodology is a reasonable approach. The

better understand the high efficiency with Born Oppenheimer is an approximation to simplify complexbetter understand the high efficiency with Born Oppenheimer is an approximation to simplify complex Figure 6 (below) gives four equations adopted by Hasewhich energetic hydrogen can transfer energy molecular systems The basis of the Born Oppenheimer is that Figure 6 (below) gives four equations adopted by Hase which energetic hydrogen can transfer energy, molecular systems. The basis of the Born Oppenheimer is that and coworkers to generate a normal mode sampling. NMS

super energy transfer To ensure a random nuclei move so much slower compared to the electrons in aand coworkers to generate a normal mode sampling. NMS is abo t setting p the initial positions and motion of thesuper energy transfer. To ensure a random

i i i l di d N l M dnuclei move so much slower compared to the electrons in a

l l h h l l i i h i iis about setting up the initial positions and motion of the

initial coordinates and momenta Normal Mode molecule that the electrons can always maintain their optimum atoms of the molecule along each of the vibrationalinitial coordinates and momenta Normal Mode S li (NMS) i d t t i iti l

molecule that the electrons can always maintain their optimum ti t h h f th l i iti [4] Thi th

atoms of the molecule along each of the vibrational di t Th t j t d t b i l h iSampling (NMS) is used to generate initial motion at each change of the nuclei position.[4] This way the coordinates. The trajectory does not obey simply harmonic Sa p g ( S) s used to ge e ate t a

t Th t j t i l d fo o a eac c a ge o e uc e pos o [ ] s ay el t i d d l l iti [4] Th l

j y y p ymotion as the molecule only obeys the quantum computedparameters. The trajectories are analyzed for electronic energy depends only on nuclear position.[4] The goal motion as the molecule only obeys the quantum computed p j y

high and efficient energy transfer Accuratelygy p y p [ ] g

of the methods used is to understand the chemical mechanism forces that each atom experiences as a function of theFi 5 ( b ) di l th ltihigh and efficient energy transfer. Accurately of the methods used is to understand the chemical mechanism forces that each atom experiences as a function of the position of each atom incl ding the h drogen [7]Figure 5 (above) displays the resulting cross g gy y

modeling the reaction pathways of hot of collisions with hot hydrogen atom reacting with energetic position of each atom including the hydrogen.[7]g ( ) p y gsections from our calculations using severalmodeling the reaction pathways of hot of collisions with hot hydrogen atom reacting with energetic sections from our calculations using several

hydrogen atom and carbon dioxide may lead molecules The figure on the rightdifferent parameters. Schatz cross is calculatedhydrogen atom and carbon dioxide may lead molecules. The figure on the right different parameters. Schatz cross is calculated f hi PES d Fl ’ i i t lto fundamental knowledge about high energy represents the Normal from his own PES and Flynn’s is experimental to fundamental knowledge about high energy p

Mode Sampling of COy

results from his laser diode experimentscollisions and the efficient activation of Mode Sampling of CO2. results from his laser diode experiments. Lit t l f R f [6]collisions and the efficient activation of

b di id Fi 1 The energy in equationLiterature values are from Ref [6]. carbon dioxide. Figure 1 The energy in equation

i ld f i di id l[ ]

carbon dioxide. g(Right) shows yields for an individual (Right) shows h i l Fi 4 (Ab ) d t t th f l l ti f i l

yenergy for a quantumthe potential Figure 4 (Above) demonstrates the force calculation for a single energy for a quantum p

energy surfaceg ( ) g

trajectory A trajectory can incorporate 1000 steps harmonic oscillator. energy surface trajectory. A trajectory can incorporate 1000 steps. Equation 2 represents theof OH + CO Equation 2 represents the

DISCUSSIONof OH + CO. Th d li t total energy of theDISCUSSIONThe red line at total energy of the

ill t E ti 3DISCUSSIONthe top oscillator. Equation 3 the top

hq

calculates the displacementThe hydrogen carbon dioxide collision can cause substantialrepresents the calculates the displacement

fThe hydrogen carbon dioxide collision can cause substantial ib ti l t f Fi 5 h th lti

penergy of the of the atoms in the normal

vibrational energy transfer. Figure 5 shows the resulting cross energy of the coordinate system for thegy g g

section of the CO 001 excitation The 001 excitation representsHydrogen coordinate system for the section of the CO2 001 excitation. The 001 excitation represents Hydrogen

2 1 V f th oscillator which is added tozero excitation in both bending and symmetric stretch and one2.1eV from the oscillator which is added to

th ilib i di tzero excitation in both bending and symmetric stretch and one q anta of e citation in the as mmetric stretch Fig re 5 sho sphotolysis of the equilibrium coordinates. quanta of excitation in the asymmetric stretch. Figure 5 shows photolysis of

HB Fiq

Equation 4 calculates theslight disargment and future work is directed towards optimizingHBr. Figure Equation 4 calculates the

fslight disargment and future work is directed towards optimizing t O t t t di h dd d N l M d

gadopted from momentum for the

parameters. Our most recent studies have added a Normal Mode adopted from oscillator R is a randomp

Sampling to generate the initial parameters for our CO moleculeLi and oscillator. Ri is a random Sampling to generate the initial parameters for our CO2 molecule Li and

C k [5] uniform number from zeroand the hydrogen atom. Sampling randomly distributes the carbonCoworkers.[5] uniform number from zero

t Thi tand the hydrogen atom. Sampling randomly distributes the carbon dio ide’s ero point energ into its fo r ibrational modes In

[ ]to one. This sets up a

dioxide’s zero point energy into its four vibrational modes. In p

realistic sample of the initialCONCLUSIONSFigure 6 equation 1 samples the energy of each mode and

realistic sample of the initial CONCLUSIONSFigure 6 equation 1 samples the energy of each mode and

ti 2 di t ib t th i t ki ti d t ti lvibrational motion.

METHODS CONCLUSIONSequation 2 distributes the energy into kinetic and potential

METHODS q gy p

energy [7] Equation 3 and 4 is multiplied by a factor of cosine andMETHODS energy.[7] Equation 3 and 4 is multiplied by a factor of cosine and METHODS sine.[7] Trigonometric factor takes into account for the phase of Collisions of hydrogen atom with CO2 molecules can depositssine.[7] Trigonometric factor takes into account for the phase of

hich a harmonic oscillator ibrates As seen b Fig re 6 aCollisions of hydrogen atom with CO2 molecules can deposits

b i l ib i l Th NMS ll f d liwhich a harmonic oscillator vibrates. As seen by Figure 6 a Data was collected by applying Born Oppenheimer Molecular Dynamics. The substantial vibrational energy. The NMS allows for a random samplingsimple diagram of the oscillations of CO2 are illustrated The plot

Data was collected by applying Born Oppenheimer Molecular Dynamics. The computations were done with the B3LYP hybrid density functional and the 6

substantial vibrational energy. The NMS allows for a random sampling f th i iti l t Th f lli i li h d t tsimple diagram of the oscillations of CO2 are illustrated. The plot

i Fi 3 i th b t i t h th H d t icomputations were done with the B3LYP hybrid density functional and the 6- of the initial parameters. The few collisions accomplish demonstrate

in Figure 3 gives the best picture on how the Hydrogen atom is 311+G(d p) basis set using Gaussian 09 (Rev C ) Initial parameters of positionp p

o r methodolog b t in order to achie e a statistical anal sis moreg g p y ginteracting The curve in the upper right corner represents the

311+G(d,p) basis set using Gaussian 09 (Rev. C.). Initial parameters of position d f th CO l l t d b i i l N l

our methodology but in order to achieve a statistical analysis more interacting. The curve in the upper right corner represents the and energy for the CO2 molecule were generated by a microcanonical Normal gy y

trajectories need to be calculated A larger sample size is beingstarting position of the Hydrogen atom. A majority of the collisionsgy 2 g y

Mode Sampling (NMS) [7] Energy for the hydrogen atom was determined by trajectories need to be calculated. A larger sample size is being starting position of the Hydrogen atom. A majority of the collisions prod ced a lo er energ transfer as seen b the color coding in

Mode Sampling (NMS).[7] Energy for the hydrogen atom was determined by j g p gcalculated in current workproduced a lower energy transfer as seen by the color coding in the photolysis of hydrogen bromide at 193 nm, which generates 51 kcal/mole. calculated in current work.

Figure 3 Higher vibrational energy transfers show a more erraticthe photolysis of hydrogen bromide at 193 nm, which generates 51 kcal/mole. The hydrogen atom is placed at a fixed location away from the target molecule Figure 3. Higher vibrational energy transfers show a more erratic

t j t f th H d t Thi ti ti ld l bThe hydrogen atom is placed at a fixed location away from the target molecule.

REFERENCEStrajectory of the Hydrogen atom. This erratic motion could also be In order to ensure a distribution of data the starting position of the Hydrogen REFERENCES

j y y gassociated with the formation of intermediates

In order to ensure a distribution of data the starting position of the Hydrogen t i d i d f 0o t 90o ith t t th t f f th REFERENCESassociated with the formation of intermediates.atom is randomized from 0o to 90o with respect to the center of mass of the p

target molecule Another randomized angle is given for the approach of the

CONTACTtarget molecule. Another randomized angle is given for the approach of the

1 Shi C Y ; Ren L ; Kong F A Chemical reaction and energy transfer between hot H atoms and CO2 molecules Chinese Journal of Chemical Physics 2006 CONTACTHydrogen atom. Both angles used 1 cosine sampling to generate the value. 1. Shi, C. Y.; Ren, L.; Kong, F. A., Chemical reaction and energy transfer between hot H atoms and CO2 molecules. Chinese Journal of Chemical Physics 2006,19 (6) 473 477 CONTACTHydrogen atom. Both angles used 1 cosine sampling to generate the value.

The cosine sampling is shown in Figure 2 The symmetry of CO allowed for19 (6), 473-477.2 C S O S S O S SO C O C C S O S CO S O S OThe cosine sampling is shown in Figure 2. The symmetry of CO2 allowed for 2. Wight, C. A.; Leone, S. R., VIBRATIONAL-STATE DISTRIBUTIONS AND ABSOLUTE EXCITATION EFFICIENCIES FOR T-V TRANSFER COLLISIONS OF

all calculations to be carried out in the first quadrant in the x-y plane with the NO AND CO WITH H-ATOMS PRODUCED BY EXCIMER LASER PHOTOLYSIS. Journal of Chemical Physics 1983, 79 (10), 4823-4829.Temple University

all calculations to be carried out in the first quadrant in the x y plane with the t t l l th i i

y , ( ),3 Tian X F ; Gao T ; He N ; Zhang Z H Ab initio molecular dynamics studies of the OH + D-2 -> HOD plus D reaction: Direct classical trajectory calculations Temple Universitytarget molecules as the origin. 3. Tian, X. F.; Gao, T.; He, N.; Zhang, Z. H., Ab initio molecular dynamics studies of the OH + D 2 > HOD plus D reaction: Direct classical trajectory calculations by MP2 Chemical Physics 2008 354 (1 3) 142 147 Benjamin Datko

g g by MP2. Chemical Physics 2008, 354 (1-3), 142-147.4 Lowe P J Quantum Chemistry Academic Press: New York 1978; p 599 Benjamin Datko4. Lowe, P. J., Quantum Chemistry. Academic Press: New York, 1978; p 599.

C (2012) Q f O CO CO(2) Tuc20805@temple.edu5. Li, J., Xie, C., Ma, J., Wang, Y., Dawes, R., Xie, D., Bowman, J. M., et al. (2012). Quasi-classical trajectory study of the HO + CO → H + CO(2) reaction on a Tuc20805@temple.eduD J th S ith

new ab initio based potential energy surface. The Journal of chemical physics, 137(2), 302278. doi:10.1063/1.4733334Dr. Jonathan Smith

p gy p y , ( ),6 Schatz G C ; Fitzcharles M S ; Harding L B STATE-TO-STATE CHEMISTRY WITH FAST HYDROGEN-ATOMS - REACTION AND COLLISIONAL Dr. Jonathan Smith

J ith1@t l d6. Schatz, G. C.; Fitzcharles, M. S.; Harding, L. B., STATE TO STATE CHEMISTRY WITH FAST HYDROGEN ATOMS REACTION AND COLLISIONAL EXCITATION IN H+CO2 Faraday Discussions 1987 84 359 369

Poster Design & Printing by Genigraphics® - 800.790.4001 Jmsmith1@temple.eduEXCITATION IN H+CO2. Faraday Discussions 1987, 84, 359-369.7 Hase L William and Buckowski G Danie Monte Carlo Sampling of Microcanical Ensemble of Classical Harmonic Oscillators Chemical Physics Lettersg g y g p @ p7. Hase, L. William and Buckowski, G. Danie., Monte Carlo Sampling of Microcanical Ensemble of Classical Harmonic Oscillators. Chemical Physics Letters1980 28 281980, 74, 284-287.