Dynamics of Reactive Collisions: The H +H2 Exchange Reaction

Karplus, Martin; Porter, Robert H.; Sharma, Renuka

doi:10.1063/1.1725438

Cited by 121 publications

(56 citation statements)

References 11 publications

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“…(i) Classical equations of motion are easy to solve; classical molecular dynamics is widely used by theorists and experimentalists for systems of up to hundreds of thousands of atoms. [21,22] Given that wavefunctions are highly oscillatory close to the classical h ! 0 limit, a trajectory representation appears more appropriate for the nuclei, than traditional grid or basis representations of wavefunctions of heavy particles.…”

Section: Introductionmentioning

confidence: 99%

Approximate quantum trajectory dynamics for reactive processes in condensed phase

Garashchuk

Jakowski

Rassolov

2014

Molecular Simulation

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A method of molecular dynamics with quantum corrections, practical for studies of large molecular systems, is reviewed. The approach is based on the Bohmian formulation of the time-dependent Schrödinger equation in which a wavefunction is represented by an ensemble of interdependent trajectories. The quantum effects come from the quantum potential acting on trajectories on par with the usual classical potential. The quantum potential is determined from the evolving nuclear wavefunction, i.e. from the quantum trajectory (QT) ensemble itself. For practical and conceptual reasons the quantum potential and corresponding quantum nuclear effect are computed only for the selected light nuclei. For studies of reactive chemical processes, the classical potential is computed on-the-fly using the density functional tight binding method of electronic structure. A massively parallel implementation, based on the message passing interface allows for efficient simulations of ensembles of thousands of trajectories describing systems of up to 200 atoms. As a biochemical application, the approximate QT approach is used to model the tunnelling-dominated proton transfer in soybean-lipoxygenase-1. A materials science application is represented by a study of the nuclear quantum effect on adsorption of hydrogen and deuterium on a C 37 H 15 molecule, which is a model 'flake' of graphene.Keywords: quantum effect; hybrid dynamics of quantum/classical nuclei; on-the-fly electronic structure; densityfunctional tight-binding method

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Section: Introductionmentioning

confidence: 99%

Approximate quantum trajectory dynamics for reactive processes in condensed phase

Garashchuk

Jakowski

Rassolov

2014

Molecular Simulation

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“…Analytical classical calculations of cross sections for ionization processes were published in the following years [3,4]. The first application of a statistical classical method to calculate cross sections in collision processes was presented by Karplus et al [5,6]. The CTMC-method as such was developed and first applied to the ionization of hydrogen by protons by Abrines and Percival [7,8].…”

Section: Introductionmentioning

confidence: 99%

Calculation of ionization of helium by relativistic heavy ions with a relativistic CTMC-method

Hofstetter

Grün

Scheid

1996

Z Phys D - Atoms, Molecules and Clusters

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“…1,2 However, for heavy particles such as nuclei, classical dynamics whose cost scales linearly with the systems size is often accurate and insightful. 3 Classical dynamics methods have been used to study systems of thousands of atoms, 4 whereas the largest reactive scattering study has been performed for a system of just five atoms-collision of hydrogen and methane. 5,6 We are interested in quantum effects on dynamics for intermediate size systems, where classical dynamics describes general behavior, but the quantummechanical (QM) effects such as tunneling and zero-pointenergy (ZPE) are important for a few light particles, e.g., protons.…”

Section: Introductionmentioning

confidence: 99%

Incorporation of quantum effects for selected degrees of freedom into the trajectory-based dynamics using spatial domains

Garashchuk

Volkov

2012

The Journal of Chemical Physics

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The approach of defining quantum corrections on nuclear dynamics of molecular systems incorporated approximately into selected degrees of freedom, is described. The approach is based on the Madelung-de-Broglie-Bohm formulation of time-dependent quantum mechanics which represents a wavefunction in terms of an ensemble of trajectories. The trajectories follow classical laws of motion except that the quantum potential, dependent on the wavefunction amplitude and its derivatives, is added to the external, classical potential. In this framework the quantum potential, determined approximately for practical reasons, is included only into the "quantum" degrees of freedom describing light particles such as protons, while neglecting with the quantum force for the heavy, nearly classical nuclei. The entire system comprised of light and heavy particles is described by a single wavefunction of full dimensionality. The coordinate space of heavy particles is divided into spatial domains or subspaces. The quantum force acting on the light particles is determined for each domain of similar configurations of the heavy nuclei. This approach effectively introduces parametric dependence of the reduced dimensionality quantum force, on classical degrees of freedom. This strategy improves accuracy of the quantum force and does not restrict interaction between the domains. The concept is illustrated for two-dimensional scattering systems, where the quantum force is required to reproduce vibrational energy of the quantum degree of freedom.

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Dynamics of Reactive Collisions: The H +H2 Exchange Reaction

Cited by 121 publications

References 11 publications

Approximate quantum trajectory dynamics for reactive processes in condensed phase

Approximate quantum trajectory dynamics for reactive processes in condensed phase

Calculation of ionization of helium by relativistic heavy ions with a relativistic CTMC-method

Incorporation of quantum effects for selected degrees of freedom into the trajectory-based dynamics using spatial domains

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