TY - JOUR
T1 - Nonadiabatic eigenvalues and adiabatic matrix elements for all isotopes of diatomic hydrogen
AU - Schwartz, Carey
AU - Le Roy, Robert J.
N1 - Funding Information:
We are pleasedt o acknowledgev ery helpful discussionsw ith Dr. A. J. Tbakker,D r. W. J. Meatb, Dr. J. F. Ogilvie,a nd Dr. D. M. Bishop,a nd thankD r. L. M. Cbeunga nd Dr. J. Rychlewskfi or providing us with unpublishedre sultsW. e area lsov eryg ratefutlo Dr. M.-C. Chuangf or bringingt o our attentiona n errori n our treatmenot f the masss calingo f tbe nonadiabaticco rrectionsT. bis work wass upportedb y the NaturalS ciencesa nd EngineeringR esearchC ouncil of Canada.
PY - 1987/2
Y1 - 1987/2
N2 - For all bound and quasibound levels of the ground electronic state of all six isotopes of diatomic hydrogen, wavefunctions obtained from the most recent ab initio potentials are used to calculate expectation values of the nuclear kinetic energy, of various powers of R, and of the average polarizability and polarizability anisotropy, together with the off-diagonal matrix elements of the polarizability required for predicting the intensities of Raman transitions for ΔJ = 0, ±2 and Δv = 0, -1, and -2. A scaling procedure for treating the nonadiabatic eigenvalue corrections is developed, which allows an extrapolation beyond results reported for H2, HD, and D2 to yield nonadiabatic level shift predictions for the three tritium isotopes. Features of this procedure which take account of implicit centrifugal distortion effects lead to significant improvements in the agreement between theory and experiment.
AB - For all bound and quasibound levels of the ground electronic state of all six isotopes of diatomic hydrogen, wavefunctions obtained from the most recent ab initio potentials are used to calculate expectation values of the nuclear kinetic energy, of various powers of R, and of the average polarizability and polarizability anisotropy, together with the off-diagonal matrix elements of the polarizability required for predicting the intensities of Raman transitions for ΔJ = 0, ±2 and Δv = 0, -1, and -2. A scaling procedure for treating the nonadiabatic eigenvalue corrections is developed, which allows an extrapolation beyond results reported for H2, HD, and D2 to yield nonadiabatic level shift predictions for the three tritium isotopes. Features of this procedure which take account of implicit centrifugal distortion effects lead to significant improvements in the agreement between theory and experiment.
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U2 - 10.1016/0022-2852(87)90059-2
DO - 10.1016/0022-2852(87)90059-2
M3 - Article
AN - SCOPUS:45949123287
SN - 0022-2852
VL - 121
SP - 420
EP - 439
JO - Journal of molecular spectroscopy
JF - Journal of molecular spectroscopy
IS - 2
ER -