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Short-time dynamics through conical intersections in macrosystems. II. Applications
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 fi...

Short-time dynamics through conical intersections in macrosystems. I. Theory: Effective-mode formulation

J. Chem. Phys. 124, 144103 (2006); doi:10.1063/1.2183304

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
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 "system" part carrying a limited number of modes, and an "environment" part. An orthogonal transformation in the environment's space is introduced, as a result of which a subset of three effective modes can be identified which couple directly to the electronic subsystem. Together with the system's modes, these govern the short-time dynamics of the overall macrosystem. The remaining environmental modes couple, in turn, to the effective modes and become relevant at longer times. In this paper, we present the derivation of the effective Hamiltonian, first introduced by Cederbaum et al. [Phys. Rev. Lett. 94, 113003 (2005)], and analyze its properties in some detail. Several special cases and topological aspects are discussed. ©2006 American Institute of Physics
History: Received 9 December 2005; accepted 10 February 2006; published 10 April 2006
Permalink: http://link.aip.org/link/?JCPSA6/124/144103/1
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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
  • 31.50.Df
    Potential energy surfaces for excited electronic states (atoms and molecules)
  • YEAR: 2006

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