Journal of Chemical Physics, Vol.110, No.17, 8448-8460, 1999
Photodissociation of HOBr. I. Ab initio potential energy surfaces for the three lowest electronic states and calculation of rotational-vibrational energy levels and wave functions
Potential energy surfaces are presented for the three lowest lying singlet electronic states of HOBr. The surfaces are computed using the recently developed multireference averaged quadratic coupled clusters method and a TZ2P orbital basis set. They provide the basic data needed to compute the dynamics of the HOBr + h nu --> OH + Br photodissociation process, which plays a key role in the bromine chemistry of the stratosphere. A pseudopotential is used for the core electrons of the Br atom; this is shown not to introduce any errors in the shape of the surfaces through direct comparison with sample all-electron calculations. Transition dipole moment surfaces for the two excitation processes (1 (1)A " <-- (X) over tilde (1)A' and 2 (1)A' <-- (X) over tilde (1)A') are also presented. These are computed using a multireference singles and doubles configuration interaction method. A grid based method is developed to compute the vibrational-rotational states of the molecule and spectroscopic constants extracted from the computed molecular energy level spacings are compared with experimentally determined quantities.