SPIN-ORBIT INTERACTIONS FROM SELF-CONSISTENT-FIELD WAVE-FUNCTIONS

Effects of the spin-orbit Hamiltonian H(LS), including both the spin-same orbit and spin-other orbit terms, are studied at the self consistent field (SCF) level of theory. Separate calculations are carried out for each state considered, and biorthogonal orbitals are constructed for the evaluation of matrix elements. Doublet-doublet and singlet-triplet interactions are discussed. The evaluation of the Gaussian basis function integrals is described in a Cartesian component representation, these integrals being directly related to one and two electron second derivative integrals. This new SCF spin-orbit code is used to (i) determine the spatial dependence of the spin orbit parameters for the Renner-Teller B-2(1), 2A1 states of H2O+, (ii) determine the spin orbit splitting of the 2PI states of OH as a function of bond-length and (iii) calculate the radiative lifetime of the a3SIGMA+ state of NO+. In each case these calculations are compared with more sophisticated configuration interaction studies, but it is found that the evaluation of these effects near equilibrium geometries at the SCF level is sufficiently accurate, provided that a large basis set is used.