Theoretical study of the spin-orbit coupling constants of the c(2p)3Πu, d(3p)3Πu, k(4p)3Πu, i(3d)3Πg, r(4d)3Πg, j(3d)3Δg, and (4f)3Δu states of H2

Abstract

Theoretical spin-orbit coupling constants as a function of internuclear distance A(R), are reported for the c(2p)3Πu, d(3p)3Πu, k(4p)3Πu, i(3d)3Πg, r(4d)3Πg, j(3d)3Δg, and (4f)3Δu states of H2. Full configuration-interaction wave functions and large Slater-type basis (STO) sets were used. A 14σ14π8δ2φ basis set optimized for the c3Πu state was used in all 3Π state calculations and a 14σ12π8δ2φ basis set optimized for the j 3Δg state was used in the 3Δ calculations. The A(R) were vibrationally averaged using our theoretical potentials. In addition, we used the more accurate c3Πu and i3Πg theoretical potentials of Kolos and Rychlewski [J. Mol. Spectrosc. 66, 428 (1977)], and for the d3Πu state a potential derived from the experimental data of Dieke [J. Mol. Spectrosc. 2, 494 (1958)]. The resulting theoretical Av values (MHz) for the v = 0, N = 1 rovibrational level compare with the experimental values (in parenthesis) as follows: c(2p)3Πu: −3887.22(−3740.987); d(3p)3Πu: −863.85 (−814.5); k(4p)3Πu: −398.8 (−306.7); i(3d)3Πg: −144.59 (−146); j(3d)3Δg: −400.82 (−409). The corresponding theoretical values for the r(4d)3Πg and (4f)3Δu states, for which no experimental data exist, are −47.1 and −114.78 MHz, respectively. These values, as well as the calculated Av for many of the higher vibrational levels, should be useful in future experimental work.