Abinitiocalculations of radiative transition probabilities in SH, SH+, and SHminus;

摘要

Potential energy and dipole moment functions for the ground states of SH, SH+, and SHminus;have been calculated from highly correlated electronic wave functions. The electric dipole moments in the vibrational ground states of32SH,32SH+, and32SHminus;are calculated to be 0.74, 1.29, and 0.27 D, and the rotationless rates of spontaneous emission thinsp;A10to be 1,thinsp; 52, and 75 sminus;1, respectively. The predicted transition probabilities between the low lying vibrational states of the electronic ground state of SH and SD are among the smallest so far known for dipole allowed rotationhyphen;vibration transitions. The calculatedAndash;Xtransition probabilities in SH confirm recent indirect determinations of the radiative lifetimes and absorption oscillator strengths in the predissociatingvrsquo;=0 level of theAstate. The4Sgr;minus;state is calculated to intersect theAthinsp;2Sgr;+state atR=3.1 a.u., between the classical turning points ofvrsquo;=0 and 1 in theAstate.