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

Download full text files

Export metadata

  • Export Bibtex
  • Export RIS

Additional Services

Share in Twitter Search Google Scholar
Metadaten
Author:Ian R. Craig, Michael Thoss, Haobin Wang
URN:urn:nbn:de:bvb:29-opus-37904
Title of the journal / compilation:Journal of Chemical Physics 135.6 (2011): 06.11.2012 <http://jcp.aip.org/resource/1/jcpsa6/v135/i6/p064504_s1>
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 -ohne weitere Spezifikation-
Dewey Decimal Classification:530 Physik
PACS-Classification:82.20.Pm Rate constants, reaction cross sections, and activation energies
82.20.Sb Correlation function theory of rate constants and its applications
82.20.Yn Solvent effects on reactivity
82.30.Hk Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange)
Collections:Allianzlizenzen 2011

$Rev: 12793 $