Spin-orbit branching in the photodissociation of HF and DF: I. A time-dependent wavepacket study for excitation from v = 0

Abstract

The photodissociation dynamics of HF and DF, following A¹P <-- X¹S⁺ electronic excitation, are examined using time-dependent wavepacket techniques. The calculations are based on new multi-reference configuration interaction calculations of the potential energy curves and complete active space self-consistent field calculations of the off-diagonal spin-orbit coupling matrix elements. The calculated branching fraction for the formation of excited state fluorine, F^*(²P_1/2), following excitation from the ground vibrational state (v = 0) of HF, agrees well with the value of 0.41 ± 0.08 measured experimentally at 121.6 nm by Zhang et al. [J. Chem. Phys. 104, 7027 (1996)]. Predictions are made for the excited spin-orbit state branching fraction for both HF and DF over a wide range of photon excitation energies. The results for HF and DF are discussed in context with the corresponding results for the photodissociation of HCl and DCl.

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