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Title: Communication: Theoretical prediction of the importance of the {sup 3}B{sub 2} state in the dynamics of sulfur dioxide

Even though the sulfur dioxide molecule has been extensively studied over the last decades, its photo-excitation dynamics is still unclear, due to its complexity, combining conical intersections, and spin-orbit coupling between a manifold of states. We present a comprehensive ab initio study of the intersystem crossing of the molecule in the low energy domain, based on a wave-packet propagation on the manifold of the lowest singlet and triplet states. Furthermore, spin-orbit couplings are evaluated on a geometry-dependent grid, and diabatized along with the different conical intersections. Our results show for the first time the primordial role of the triplet {sup 3}B{sub 2} state and furthermore predict novel interference patterns due to the different intersystem crossing channels induced by the spin-orbit couplings and the shapes of the different potential energy surfaces. These give new insight into the coupled singlet-triplet dynamics of SO{sub 2}.
Authors:
 [1] ;  [2] ;  [3] ;  [1] ;  [2] ;  [4]
  1. Sorbonne Universités, UPMC Univ. Paris 06, Laboratoire de Chimie Physique-Matière et Rayonnement, UMR 7614, 11 Rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France)
  2. (France)
  3. (Germany)
  4. Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg (Germany)
Publication Date:
OSTI Identifier:
22255014
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 9; Other Information: (c) 2014 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; EXCITATION; L-S COUPLING; POTENTIAL ENERGY; SULFUR DIOXIDE; SURFACES; TRIPLETS