Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 116, Issue 11, Pages 2629-2635Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp2068528
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Funding
- TAMOP [4.2.1./B-09/1/KONV-2010-0007]
- COST Action [CM0702 CUSPFEL]
- Deutsche Forschungsgemeinschaft
- John-von-Neumann Institute, Research Centre Juelich [ehu01]
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We present a detailed study for the short-time dynamics through conical intersections in molecular systems related to the quadratic vibronic coupling (QVC) Hamiltonian [Muller, H.; Koppel, H.; Cederbaum, L. S. New J. Chem. 1993, 17, 7-29] and the effective-mode formalism [Cederbaum, L. S.; Gindensperger, E.; Burghardt, I. Phys. Rev. Lett. 2005, 94, 113003]. Our approach is based on splitting the nuclear degrees of freedom of the whole system into system modes and environment modes. It was found that only three-effective environmental modes together with the system's modes are needed to describe the short-time dynamics of the complex system correctly. In addition, a detailed mathematical proof is given in the appendix to demonstrate that the exact cumulants are recovered up to the second order within the cumulant expansion of the autocorrelation function. The butatriene molecule is studied as an explicit showcase example to stress the viability of our proposed scheme and to compare with other systems.
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