Abstract
The mechanism for predissociation of the vinoxy radical after the excitation X̃ 2A″→B̃ 2A″ is studied theoretically. Critical points on the à 2A′ and B̃ 2A″ potential energy surfaces are determined at the multireference configuration interaction level using expansions of five million configuration state functions. A mechanism consisting of a sequence of internal conversions to the ground state is proposed. B̃ 2A″–à 2A′ conical intersections are shown to be too high in energy to participate in this process. The B̃ 2A″–à 2A′ radiationless transition is enabled by an avoided crossing which is accessible after a barrier of ca. 2000 cm−1, in agreement with experimental observations. Subsequently the à 2A′→X̃ 2A″ radiationless transition can occur very efficiently through easily accessible conical intersections. A one-dimensional coupled adiabatic state model of the process is developed. The radiationless decay rates of the vibrational levels obtained from this model serve to validate the proposed mechanism.
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