A b i n i t i o studies of the photodissociation in the first excited states of à 1A1 and ã 3A1 of PH3

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Abstract
HF and CI calculations were carried out to explain the predissociation process in the first excited à 1A1 state of PH3 that is observed experimentally. It is found that the mechanism of the predissociation involves Rydberg-valence transformation leading to the production of PH2(X̃ 2B1, à 2A1) and H(2S). This process is similar to that found in the first excited 1A2′′ state of NH3; however, the thermodynamics of the two processes are different. A corresponding study for the PH3(ã 3A1) reveals a major difference from the 3A2′′ of NH3 due to the absence of the Rydberg character of the PH3(ã 3A1) at the equilibrium geometry. In addition, we report HF calculations on the equilibrium bond distances and the angles, the vibrational frequencies and the barriers to inversion of the neutral ground state of PH3(X̃ 1A1), its first singlet and triplet excited states (à 1A1 and ã 3A1, respectively), and the ground state ion (X̃ 2A1).

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