Rotation–vibrational analysis for three states of NaH and NaD

Abstract

We have carried out a rotation–vibrational analysis for the X1Σ+, A1Σ+, and b3Π states of NaH and NaD using accurate ab initio calculated potential curves. The calculated values of Be, αe, Re, ωe, and ωexe (with known experimental values in parentheses) are NaH X1Σ+ : Be = 4.748 (4.886) cm−1, αe = 0.126 (0.129) cm−1, Re = 3.625 (3.562) bohr, ωe = 1183.17 (1172.2) cm−1, and ωexe = 21.23 (19.72) cm−1; NaD X1Σ+ : Be = 2.475 (2.5575) cm−1, αe = 0.0474 (0.0520) cm−1, Re = 3.624 (3.565) bohr, ωe = 826.60 (826.10) cm−1 and ωexe = 9.44 cm−1; NaH b3Π : Be = 3.533 cm−1, αe = 0.853 cm−1, Re = 4.202 bohr, ωe = 419.39 cm−1 and ωexe = 50.25 cm−1; NaD b3Π: Be = 1.763 cm−1, αe = 0.265 cm−1, Re = 4.294 bohr, ωe = 311.95 cm−1 and ωexe = 28.68 cm−1. The anomalous behavior of the Bv′s and ΔGv+1/2′s of the A1Σ+ state is satisfactorily reproduced by these calculations: for NaH, Bv (max ) = 1.9717 (1.941) cm−1 at v = 6 (6) and ΔGv+1/2 (max) = 381.37 (360.3) cm−1 at v = 9 (8); for NaD, Bv (max) = 1.0274 (1.012) cm−1 at v = 8 (8) and ΔGv+1/2 (max) = 275.34 (260.22) cm−1 at v = 13 (12). The wavefunctions obtained were also used to calculate average electric dipole moments resulting in the following values (for the lowest rotation–vibrational states): for NaH, μe (X1Σ+) = 2.674 a.u., μe (A1Σ+) = 0.189 a.u., and μe (b3Π) = 0.158 a.u., for NaD, μe (X1Σ+) = 2.668 a.u., μe (A1Σ+) = 0.178 a.u., and μe (b3Π) = 0.163 a.u.