TY - JOUR
T1 - Isotopic dependence of Born-Oppenheimer breakdown effects in diatomic hydrides
T2 - The X1Σ+ states of HI DI and HBr DBr
AU - Coxon, John A.
AU - Hajigeorgiou, Photos G.
PY - 1991
Y1 - 1991
N2 - Line positions available from literature data for HI DI and HBr DBr have been employed to determine corrections to the Born-Oppenheimer approximation. For the ground X1Σ+ states of HI and DI, an analytical effective nonadiabatic Hamiltonian with 13 fitted parameters describes experimental observables within the precision of the measurements. The analytical operator for the X1Σ+ states of HBr and DBr is defined by 12 fitted parameters and achieves similar success. Rotational and centrifugal distortion constants are determined a posteriori through perturbation theory; along with the rotationless eigenvalues, they represent the spectroscopic line positions to within the precision of the measurements. Quantum-mechanical molecular constants are also calculated for TI, T79Br, and T81Br. A detailed study of the isotopic variation of Re values in hydrogen halide ground states is made using the existing theory.
AB - Line positions available from literature data for HI DI and HBr DBr have been employed to determine corrections to the Born-Oppenheimer approximation. For the ground X1Σ+ states of HI and DI, an analytical effective nonadiabatic Hamiltonian with 13 fitted parameters describes experimental observables within the precision of the measurements. The analytical operator for the X1Σ+ states of HBr and DBr is defined by 12 fitted parameters and achieves similar success. Rotational and centrifugal distortion constants are determined a posteriori through perturbation theory; along with the rotationless eigenvalues, they represent the spectroscopic line positions to within the precision of the measurements. Quantum-mechanical molecular constants are also calculated for TI, T79Br, and T81Br. A detailed study of the isotopic variation of Re values in hydrogen halide ground states is made using the existing theory.
UR - http://www.scopus.com/inward/record.url?scp=0010025366&partnerID=8YFLogxK
U2 - 10.1016/0022-2852(91)90189-H
DO - 10.1016/0022-2852(91)90189-H
M3 - Article
AN - SCOPUS:0010025366
SN - 0022-2852
VL - 150
SP - 1
EP - 27
JO - Journal of Molecular Spectroscopy
JF - Journal of Molecular Spectroscopy
IS - 1
ER -