Theory and ab initio calculation of partial widths and interchannel coupling in predissociating diatomic states: application to HeF

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According to previously published theory, it is possible to obtain partial widths to all orders, of multichannel decaying states, by diagonalizing relatively small, state-specific complex matrices constructed from appropriate square integrable functions of real and complex coordinates. Here, an ab initio method is presented for computing predissociating states of polyelectronic diatomic molecules. Application is made to the recently calculated 2 2 Σ + excimer state of HeF which decays to the repulsive X 2 Σ + and 1 2 Π states. It is found that for the X 2 Σ channel, the all-orders result differs from that of the golden-rule formula by an order of magnitude.