Adiabatic States Derived from a Spin-Coupled Diabatic Transformation: Semiclassical Trajectory Study of Photodissociation of HBr and the Construction of Potential Curves for LiBr+

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• 作者：Rosendo Valero ; Donald G. Truhlar ; Ahren W. Jasper
• 刊名：Journal of Physical Chemistry A
• 出版年：2008
• 出版时间：June 26, 2008
• 年：2008
• 卷：112
• 期：25
• 页码：5756 - 5769
• 全文大小：232K
• 年卷期：v.112,no.25(June 26, 2008)
• ISSN：1520-5215

文摘

The development of spin-coupled diabatic representations for theoretical semiclassical treatments of photodissociation dynamics is an important practical goal, and some of the assumptions required to carry this out may be validated by applications to simple systems. With this objective, we report here a study of the photodissociation dynamics of the prototypical HBr system using semiclassical trajectory methods. The valence (spin-free) potential energy curves and the permanent and transition dipole moments were computed using high-level ab initio methods and were transformed to a spin-coupled diabatic representation. The spin−orbit coupling used in the transformation was taken as that of atomic bromine at all internuclear distances. Adiabatic potential energy curves, nonadiabatic couplings and transition dipole moments were then obtained from the diabatic ones and were used in all the dynamics calculations. Nonadiabatic photodissociation probabilities were computed using three semiclassical trajectory methods, namely, coherent switching with decay of mixing (CSDM), fewest switches with time uncertainty (FSTU), and its recently developed variant with stochastic decoherence (FTSU/SD), each combined with semiclassical sampling of the initial vibrational state. The calculated branching fraction to the higher fine-structure level of the bromine atom is in good agreement with experiment and with more complete theoretical treatments. The present study, by comparing our new calculations to wave packet calculations with distance-dependent ab initio spin−orbit coupling, validates the semiclassical trajectory methods, the semiclassical initial state sample scheme, and the use of a distance-independent spin−orbit coupling for future applications to polyatomic photodissociation. Finally, using LiBr⁺ as a model system, it is shown that accurate spin-coupled potential curves can also be constructed for odd-electron systems using the same strategy as for HBr.