TY - JOUR
T1 - Isotopic dependence of Born-Oppenheimer breakdown effects in diatomic hydrides
T2 - The B1Σ+ and X1Σ+ states of HCl and DCl
AU - Coxon, John A.
AU - Hajigeorgiou, Photos G.
PY - 1990
Y1 - 1990
N2 - A numerical procedure for obtaining isotopically self-consistent radial Hamiltonian operators from spectroscopic line positions is applied to the X1Σ+ and B1Σ+ electronic states of H35Cl, H37Cl, D35Cl, and D37Cl. A simultaneous four-isotopomer, two-state least-squares fit of 8497 line positions yields Born-Oppenheimer potentials for both states and radial functions which describe adiabatic and nonadiabatic effects. Rotationally dependent energy shifts in the ground states of the four isotopomers are described by a single mass-reduced purely nonadiabatic radial function, qX(R). The assignments for the B-X system of D35Cl are extended and the first set of rotational assignments for D37Cl is presented. Synthetic calculations of the microwave line positions for TCl reproduce satisfactorily the experimental spectra.
AB - A numerical procedure for obtaining isotopically self-consistent radial Hamiltonian operators from spectroscopic line positions is applied to the X1Σ+ and B1Σ+ electronic states of H35Cl, H37Cl, D35Cl, and D37Cl. A simultaneous four-isotopomer, two-state least-squares fit of 8497 line positions yields Born-Oppenheimer potentials for both states and radial functions which describe adiabatic and nonadiabatic effects. Rotationally dependent energy shifts in the ground states of the four isotopomers are described by a single mass-reduced purely nonadiabatic radial function, qX(R). The assignments for the B-X system of D35Cl are extended and the first set of rotational assignments for D37Cl is presented. Synthetic calculations of the microwave line positions for TCl reproduce satisfactorily the experimental spectra.
UR - http://www.scopus.com/inward/record.url?scp=0040118303&partnerID=8YFLogxK
U2 - 10.1016/0022-2852(90)90244-K
DO - 10.1016/0022-2852(90)90244-K
M3 - Article
AN - SCOPUS:0040118303
SN - 0022-2852
VL - 139
SP - 84
EP - 106
JO - Journal of Molecular Spectroscopy
JF - Journal of Molecular Spectroscopy
IS - 1
ER -