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Short-time dynamics through conical intersections in macrosystems. I. Theory: Effective-mode formulation
The short-time dynamics through a conical intersection of a macrosystem comprising a large number of nuclear degrees of freedom (modes) is investigated. The macrosystem is decomposed into a "syst...
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Short-time dynamics through conical intersections in macrosystems. II. Applications

J. Chem. Phys. 124, 144104 (2006); doi:10.1063/1.2183305

Published 10 April 2006

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Etienne Gindensperger
Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany

Irene Burghardt
Département de Chimie, Ecole Normale Supérieure, 24 rue Lhomond, F-75231 Paris Cedex 05, France

Lorenz S. Cederbaum
Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany
We present several numerical applications based upon the effective-mode formulation for the short-time dynamics through conical intersections in macrosystems, as detailed in the preceding paper and first proposed by Cederbaum et al. [Phys. Rev. Lett. 94, 113003 (2005)]. The macrosystem, containing a vast number of nuclear degrees of freedom (modes), is decomposed into a system part and an environment part. Only three effective environmental modes are needed—together with the system's modes—to accurately calculate the low resolution spectra and the short-time dynamics of the entire macrosystem. For the systems discussed here, results are compared to those of a full quantum wave-packet propagation. Some rules are extracted to provide general tendencies; these rules allow one to understand and predict the dynamical properties in more general situations where the exact quantum dynamics of the macrosystem is out of reach. ©2006 American Institute of Physics
History: Received 9 December 2005; accepted 10 February 2006; published 10 April 2006
Permalink: http://link.aip.org/link/?JCPSA6/124/144104/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.-p
    Calculations and mathematical techniques in atomic and molecular physics excluding electron correlation calculations
  • 33.15.Mt
    Molecular rotation, vibration, and vibration-rotation constants
  • YEAR: 2006

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0021-9606 (print)   1089-7690 (online)
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REFERENCES (26)
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