RELATIVISTIC CONFIGURATION-INTERACTION CALCULATIONS OF POTENTIAL CURVES AND RADIATIVE TRANSITION-PROBABILITIES FOR THE ANTIMONY FLUORIDE MOLECULE

An ab initio configuration interaction treatment is reported for the a ntimony fluoride molecule employing relativistic effective core potent ials (RECPs) including spin-orbit coupling. Potential curves for the l owest nine OMEGA states are obtained and good agreement with experimen tal values for bond lengths (0.01-0.02 angstrom) and vibrational frequ encies (+/- 30 cm-1) is noted. Observed multiplet splittings for X3SIG MA- and A 3PI are reproduced well in the computations, showing the reg ular order expected from the latter's pisigma* electronic configurati on; the absolute T(e) values for A-X transitions are uniformly overest imated by 1200 cm-1 (0.15 eV). Radiative transition probabilities comp uted with the corresponding vibrational wavefunctions are consistent w ith empirical rules given by Colin and co-workers for the relative int ensities of b0+-X10+, X(2)1 band systems. These results are compared w ith analogous findings for the heavier bismuth fluoride system, for wh ich an exception to the above rule has been observed, and the theoreti cal basis for these trends is discussed.