Classical trajectory study of three-body direct photofragmentation of Cd(CH 3) 2. Comparison of sampling methods

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The classical trajectory method has been used to investigate product-state symmetry in the three-body direct photofragmentation of Cd(CH 3) 2. Photon absorption was assumed to satisfy the Franck principle and relative weights for trajectory initial conditions were assigned by either the Wigner or the classical (300 K) distribution function. In qualitative agreement with earlier “quasi-classical” sampling studies of Kellman et al. for photolysis of the Cd(CH 3) 2 vibrational ground state, product-state asymmetry is found to increase with increasing photolysis wavelength. Contrary to the “quasi-classical” sampling results, however, sampling with the classical distribution function indicates that product-state symmetry is unaffected by vibrational excitation of Cd(CH 3) 2 prior to photolysis. For sampling with the Wigner distribution function, in agreement with the “quasi-classical” sampling studies, excitation of the Cd(CH 3) 2 asymmetric stretch prior to photolysis is found to increase product-state asymmetry.