Accurate quantum-mechanical rate constants for a linear response Azzouz-Borgis proton transfer model employing the multilayer multiconfiguration time-dependent Hartree approach

  • The multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method is applied to simulate the quantum dynamics and thermal rate constant of the Azzouz-Borgis model of proton transfer in a polar solvent. To this end, the original atomistic potential is mapped to a system-bath model. Employing the flux correlation function formalism and importance sampling techniques, accurate quantum mechanical rate constants are obtained, which provide a benchmark for evaluating approximate approaches to study the quantum dynamics of condensed-phase chemical reactions. Furthermore, the validity of the mapping procedure is discussed based on the comparison of the classical dynamics of the original atoThe multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method is applied to simulate the quantum dynamics and thermal rate constant of the Azzouz-Borgis model of proton transfer in a polar solvent. To this end, the original atomistic potential is mapped to a system-bath model. Employing the flux correlation function formalism and importance sampling techniques, accurate quantum mechanical rate constants are obtained, which provide a benchmark for evaluating approximate approaches to study the quantum dynamics of condensed-phase chemical reactions. Furthermore, the validity of the mapping procedure is discussed based on the comparison of the classical dynamics of the original atomistic Azzouz-Borgis model and the mapped system-bath model.show moreshow less

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Metadaten
Author:Ian R. Craig, Michael Thoss, Haobin Wang
URN:urn:nbn:de:bvb:29-opus-37904
Document Type:Article
Language:English
Date of Publication (online):2012/11/07
Publishing Institution:Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU)
Release Date:2012/11/07
Tag:chemical exchanges; configuration interactions; importance sampling; quantum chemistry; reaction kinetics theory
SWD-Keyword:-
Original publication:Journal of Chemical Physics 135.6 (2011): 06.11.2012 <http://jcp.aip.org/resource/1/jcpsa6/v135/i6/p064504_s1>
Institutes:Naturwissenschaftliche Fakultät / Naturwissenschaftliche Fakultät -ohne weitere Spezifikation-
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 53 Physik / 530 Physik
PACS-Classification:80.00.00 INTERDISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY / 82.00.00 Physical chemistry and chemical physics; Electronic structure theory of atoms and molecules, see 31.15.-p; Electronic structure theory of condensed matter, see section 71; Electronic structure theory for biomolecules, see 87.10.-e; Electronic structure of / 82.20.-w Chemical kinetics and dynamics / 82.20.Pm Rate constants, reaction cross sections, and activation energies
80.00.00 INTERDISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY / 82.00.00 Physical chemistry and chemical physics; Electronic structure theory of atoms and molecules, see 31.15.-p; Electronic structure theory of condensed matter, see section 71; Electronic structure theory for biomolecules, see 87.10.-e; Electronic structure of / 82.20.-w Chemical kinetics and dynamics / 82.20.Sb Correlation function theory of rate constants and its applications
80.00.00 INTERDISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY / 82.00.00 Physical chemistry and chemical physics; Electronic structure theory of atoms and molecules, see 31.15.-p; Electronic structure theory of condensed matter, see section 71; Electronic structure theory for biomolecules, see 87.10.-e; Electronic structure of / 82.20.-w Chemical kinetics and dynamics / 82.20.Yn Solvent effects on reactivity
80.00.00 INTERDISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY / 82.00.00 Physical chemistry and chemical physics; Electronic structure theory of atoms and molecules, see 31.15.-p; Electronic structure theory of condensed matter, see section 71; Electronic structure theory for biomolecules, see 87.10.-e; Electronic structure of / 82.30.-b Specific chemical reactions; reaction mechanisms / 82.30.Hk Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange)
Collections:Universität Erlangen-Nürnberg / Allianzlizenzen / Allianzlizenzen 2011

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