Proton transfer reactions in model condensed-phase environments: Accurate quantum dynamics using the multilayer multiconfiguration time-dependent Hartree approach

The recently proposed multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) approach to evaluating reactive quantum dynamics is applied to two model condensed-phase proton transfer reactions. The models consist of a one-dimensional double-well "system" that is bilinearly coupled...

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Bibliographic Details
Published in:The Journal of chemical physics 2007-10, Vol.127 (14), p.144503-144503
Main Authors: Craig, Ian R, Thoss, Michael, Wang, Haobin
Format: Article
Language:English
Subjects:
Chemical Sciences
Physics
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Summary:The recently proposed multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) approach to evaluating reactive quantum dynamics is applied to two model condensed-phase proton transfer reactions. The models consist of a one-dimensional double-well "system" that is bilinearly coupled to a "bath" of harmonic oscillators parameterized to represent a condensed-phase environment. Numerically exact quantum-mechanical flux correlation functions and thermal rate constants are obtained for a broad range of temperatures and system-bath coupling strengths, thus demonstrating the efficacy of the ML-MCTDH approach. Particular attention is focused on the regime where low temperatures are combined with weak system-bath coupling. Under such conditions it is found that long propagation times are often required and that quantum coherence effects may prevent a rigorous determination of the rate constant.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.2772265