Theoretical investigation of the photodissociation dynamics of HONO: Vibrational predissociation in the electronically excited state S1
1989; Elsevier BV; Volume: 129; Issue: 1 Linguagem: Inglês
10.1016/0301-0104(89)80022-9
ISSN1873-4421
AutoresSteffen Hennig, Agathe Untch, Reinhard Schinke, Mareo Nonella, J. Robert Huber,
Tópico(s)Spectroscopy and Laser Applications
ResumoWe report the results of a two-dimensional, quantum mechanical study of the photodissociation of HONO within the first continuum (S0→S1). The S0 and S1 potential energy surfaces are calculated by means of ab initio methods with variations of the ON and the NO bond lengths while keeping all other coordinates fixed at their ground state values. The dominant band of diffuse structure in the experimental absorption spectrum is unambiguously explained by scattering resonances resulting from a shallow potential well in the S1 potential energy surface. The fragmentation of the excited complex proceeds via vibrational predissociation in the upper electronic state. Particular attention is paid to the sensitive dependence of the resonance widths as well as to the NO vibrational state distributions on the vibrational-translational coupling strength. In order to elucidate the fragmentation process we performed also classical trajectory calculations. The main trends of the vibrational state distribution in the NO fragment are well reproduced.
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