Flux redistribution during the photodissociation of ClNO in the T1 state

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Abstract
The mechanism of the photofragmentation of ClNO in the first triplet state (T1) is investigated using our quantum flux method based on time‐independent calculations using a new ab initio potential. Particular attention is focused on the development of the NO rotational distributions, as a function of the Cl–NO separation and as a function of excitation wavelength. The nodal structure of the ClNO bending wavefunction in the Franck–Condon region leaves indelible traces on the evolving photofragment flux, examined in coordinate space. The structure of the flux redistribution in terms of photofragment product states is less readily interpreted. Although the final product distributions are virtually adiabatic in the NO vibrational motion, considerable excitation of NO vibrational motion does occur during the photodissociation, which later disappears into rotation as the fragments separate. This internal energy flow can be seen clearly in an analysis of the flux redistribution among the adiabatic states of the internal motion, and is a consequence of strong vibration‐rotation coupling in the Franck–Condon region. The picture obtained here of the mechanism of this complex process is complementary to that offered by earlier dynamical studies.