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Title: Reaction surface approach to multimode vibronic coupling problems: General framework and application to furan

A new general framework for treating the dynamics on intersecting multidimensional potential energy surfaces is presented. It rests on a sub-division of the nuclear coordinates into different classes, one of primary importance with large-amplitude displacements during the process of interest and another one with smaller displacements, thus permitting a more approximate description. The latter are treated within the well-known linear + quadratic vibronic coupling scheme, where, however, the expansion “coefficients” are general functions of the “primary” coordinates. This may be augmented by an effective-mode approach for further degrees of freedom acting as an environment for the dynamics of the original modes. Following the general considerations, the approach is applied to the nonadiabatic photodynamics of furan and is shown to allow for an eight-dimensional quantum treatment, of higher dimension than was possible so far. The influence of the various degrees of freedom on the dynamics and lifetime of furan due to nonadiabatic ring-opening is discussed.
Authors:
 [1] ;  [2] ; ;  [1] ;  [3]
  1. Theoretical Chemistry, Institute of Physical Chemistry, University of Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg (Germany)
  2. (Russian Federation)
  3. CTMM, Institut Charles Gerhardt, UMR 5253, CC 1501, Université Montpellier II, 34095 Montpellier, Cedex 05 (France)
Publication Date:
OSTI Identifier:
22220238
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 23; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; CHEMICAL REACTIONS; DEGREES OF FREEDOM; FURANS; POTENTIAL ENERGY; REACTION KINETICS; SURFACES