Resonances in the photodissociation of OH by absorption into coupled 2Π states: Adiabatic and diabatic formulations

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Abstract
The bound 3 2Π and repulsive 2 2Π states of OH are strongly coupled by the action of the nuclear kinetic energy operator. The process of photodissociation by absorption into the coupled 2Π states is studied theoretically. The adiabatic electronic eigenfunctions and potential energy curves of the 2 2Π and 3 2Π states are calculated using large configuration‐interaction (CI) representations and the nuclear radial coupling matrix elements are obtained by numerical differentiation. The coupled equations for the nuclear wave functions of the two states are set up in an adiabatic and in a diabatic formulation and are solved by numerical integration. The electric dipole transition moments connecting the ground X 2Π state to the 2 2Π and 3 2Π states are computed from the CI wave functions and the resulting photodissociation cross sections of OH arising from absorption into the coupled 2 2Π and 3 2Π states are obtained. Two alternative sets of potential curves, coupling matrix elements, and transition moments are employed to provide an assessment of the accuracy of the results. The photodissociation cross section shows a series of resonances superimposed on a broad continuous background. The resonances are located near to the vibrational levels of the uncoupled bound diabatic potential curve. They have asymmetric Beutler–Fano profiles and vary in width from 50 cm−1 for the lowest levels to 2 cm−1 for the higher levels. The accuracy of adiabatic and diabatic approximations, carried to first order in the coupling, is explored and it is demonstrated that the diabatic approximation provides a more satisfactory representation of the photodissociation process. The discrete‐continuum configuration interaction theory of Fano is applied in the diabatic formulation and the resonance structures are calculated. The discrete‐continuum interaction theory yields profile parameters and level shifts which agree well with the accurate values obtained by solving the coupled equations but its application is considerably more laborious. The contribution of absorption into the coupled 2Π states to the interstellar photodissociation rate is evaluated. In the optically thin limit, the rate is1.5×10−10 s−1. The total rate is 4×10−10 s−1.

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