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

Journal Article · Fri Mar 07 04:00:00 EST 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4867252· OSTI ID:22255014

Lévêque, Camille ^[1]; Taïeb, Richard ^[1]; Köppel, Horst ^[2]

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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. Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg (Germany)

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}.

• OSTI ID: 22255014
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 9 Vol. 140; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
EXCITATION
L-S COUPLING
POTENTIAL ENERGY
SULFUR DIOXIDE
SURFACES
TRIPLETS