Hyperthermal chemistry in the gas phase and on surfaces: theoretical studies

Troya, Diego; Schatz, George C.

doi:10.1080/0144235042000298484

Cited by 58 publications

(59 citation statements)

References 228 publications

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“…This direct chemical dynamics simulation approach for determining unimolecular reaction paths and Arrhenius parameters is expected to be particularly useful for large molecules with many decomposition paths, and whose TSs may be difficult to determine by standard electronic structure theory methods and whose structures are not readily obvious 116. Additional applications and tests of this computational chemistry approach for determining unimolecular decomposition pathways and Arrhenius parameters, are expected.…”

Section: Illustrative Simulationsmentioning

confidence: 99%

Direct chemical dynamics simulations: coupling of classical and quasiclassical trajectories with electronic structure theory

Paranjothy

Sun

Zhuang

et al. 2012

WIREs Comput Mol Sci

101

116

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In classical and quasiclassical trajectory chemical dynamics simulations, the atomistic dynamics of collisions, chemical reactions, and energy transfer are studied by solving the classical equations of motion. These equations require the potential energy and its gradient for the chemical system under study, and they may be obtained directly from an electronic structure theory. This article reviews such direct dynamics simulations. The accuracy of classical chemical dynamics is considered, with simulations highlighted for the F − + CH 3 OOH reaction and of energy transfer in collisions of CO 2 with a perfluorinated self-assembled monolayer (F-SAM) surface. Procedures for interfacing chemical dynamics and electronic structure theory computer codes are discussed. A Hessian-based predictor-corrector algorithm and high-accuracy Hessian updating algorithm, for enhancing the efficiency of direct dynamics simulations, are described. In these simulations, an ensemble of trajectories is calculated which represents the experimental and chemical system under study. Algorithms are described for selecting the appropriate initial conditions for bimolecular and unimolecular reactions, gas-surface collisions, and initializing trajectories at transition states and conical intersections. Illustrative direct dynamics simulations are presented for the Cl − + CH 3 I S N 2 reaction, unimolecular decomposition of the epoxy resin constituent CH 3 NH CH CH CH 3 versus temperature, collisions and reactions of N-protonated diglycine with a F-SAM surface that has a reactive head group, and the product energy partitioning for the post-transition state dynamics of C 2 H 5 F → HF + C 2 H 4 dissociation.

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Section: Illustrative Simulationsmentioning

confidence: 99%

Direct chemical dynamics simulations: coupling of classical and quasiclassical trajectories with electronic structure theory

Paranjothy

Sun

Zhuang

et al. 2012

WIREs Comput Mol Sci

101

116

View full text Add to dashboard Cite

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“…where E f,1 is the final translational energy of m 1. eqn (4), (5), and ( 6) may manipulated into the form,…”

Section: Appendix: Kinematic Modelmentioning

confidence: 99%

“…Over the past few decades, an impressive body of work has involved study of energy transfer processes during atomic and molecular collisions with liquid and self-assembled monolayer surfaces. [1][2][3][4][5][6] These studies reveal that a complicated interplay of kinematics, supramolecular structures, and potential energy landscapes influence energy transfer. The differences in atom or molecule scattering dynamics on surfaces of different composition suggest the possibility of using beam-surface scattering techniques as an analytical probe of liquid surfaces, 7,8 but the practical implementation of such techniques would benefit from straightforward methods to interpret the data.…”

Section: Introductionmentioning

confidence: 99%

Kinematics and dynamics of atomic-beam scattering on liquid and self-assembled monolayer surfaces

et al. 2012

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We have conducted investigations of the energy transfer dynamics of atomic oxygen and argon scattering from hydrocarbon and fluorocarbon surfaces. In light of these results, we appraise the applicability and value of a kinematic scattering model, which views a gas-surface interaction as a gas-phase-like collision between an incident atom or molecule and a localized region of the surface with an effective mass. We have applied this model to interpret the effective surface mass and energy transfer when atoms strike two different surfaces under identical bombardment conditions. To this end, we have collected new data, and we have re-examined existing data sets from both molecular-beam experiments and molecular dynamics simulations. We seek to identify trends that could lead to a robust general understanding of energy transfer processes induced by collisions of gas-phase species with liquid and semi-solid surfaces.

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“…Recent theoretical studies have extended these previous efforts with ab initio potentials to accurately model liquid-liquid and gas-surface interactions. For example, experimental internal state populations and translational distributions for O( 3 P) + squalane [35][36][37] have been compared with MD simulations by the Schatz group. In addition to explicit liquid surface models, selfassembled monolayer surfaces (SAMs) have been studied by MD simulations, 35,[38][39][40][41][42][43][44][45][46][47] stimulated by the liquid-like behavior observed in scattering experiments.…”

Section: Introductionmentioning

confidence: 99%

High resolution Dopplerimetry of correlated angular and quantum state-resolved CO2 scattering dynamics at the gas–liquid interface

Perkins

Nesbitt

2010

Phys. Chem. Chem. Phys.

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Full three dimensional (3D) translational distributions for quantum state-resolved scattering dynamics at the gas-liquid interface are presented for experimental and theoretical studies of CO(2) + perfluorinated surfaces. Experimentally, high resolution absorption profiles are measured as a function of incident (θ(inc)) and scattering (θ(scat)) angles for CO(2) that has been scattered from a 300 K perfluorinated polyether surface (PFPE) with an incident energy of E(inc) = 10.6(8) kcal mol(-1). Line shape analysis of the absorption profiles reveals non-equilibrium dynamics that are characterized by trapping-desorption (TD) and impulsive scattering (IS) components, with each channel simply characterized by an effective "temperature" that compares very well with previous results from rotational state analysis [Perkins and Nesbitt, J. Phys. Chem. A, 2008, 112, 9324]. From a theoretical perspective, molecular dynamics (MD) simulations of CO(2) + fluorinated self-assembled monolayer surface (F-SAMs) yield translational probability distributions that are also compared with experimental results. Trajectories are parsed by θ(scat) and J, with the results rigorously corrected by flux-to-density transformation and providing comparisons in near quantitative agreement with experiment. 3D flux and velocity distributions obtained from MD simulations are also presented to illustrate the role of in- and out-of-plane scattering.

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Hyperthermal chemistry in the gas phase and on surfaces: theoretical studies

Cited by 58 publications

References 228 publications

Direct chemical dynamics simulations: coupling of classical and quasiclassical trajectories with electronic structure theory

Direct chemical dynamics simulations: coupling of classical and quasiclassical trajectories with electronic structure theory

Kinematics and dynamics of atomic-beam scattering on liquid and self-assembled monolayer surfaces

High resolution Dopplerimetry of correlated angular and quantum state-resolved CO2 scattering dynamics at the gas–liquid interface

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