EF, GK, and HH-bar /sup 1/. sigma. /sub g//sup +/ states of hydrogen. Improved ab initio calculation of vibrational states in the adiabatic approximation
Electronic energies and diagonal energy corrections for nuclear motion are calculated for the first three excited /sup 1/..sigma../sub g//sup +/ states of H/sub 2/ at some 70 internuclear separations in the interval R(a.u.) element of)1,15). More accurate electronic wave functions comprising, respectively, 129, 118, and 110 terms for the EF, GK, and HH-bar states, and a new method for the evaluation of the relevant integrals are used. The maximum values of the adiabatic energy corrections are found to be larger than the previously published values by 60 cm/sup -1/ (EF at R = 3.2 a.u.), 55 cm/sup -1/ (GK at R = 2.85 a.u.), and 38 cm/sup -1/ (HH-bar at R = 2.95 a.u.), while the electronic energies at the same values of R are now lower by -6, -26, and -7 cm/sup -1/. The adiabatic ab initio vibrational energies of the EF, v = 0, levels lie 1.9 (H/sub 2/) and 1.4 cm/sup -1/ (HD and D/sub 2/) above the experimental values. All higher vibrational levels of the three electronic states are appreciably affected by nonadiabatic energy shifts.
- Research Organization:
- Physical Chemistry Laboratory, ETH-Zentrum, CH-8092 Zuerich, Switzerland
- OSTI ID:
- 5837649
- Journal Information:
- J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 82:7; ISSN JCPSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ADIABATIC APPROXIMATION
DEUTERIDES
DEUTERIUM
DEUTERIUM COMPOUNDS
ELECTRONIC STRUCTURE
ELEMENTS
ENERGY LEVELS
EXCITED STATES
FUNCTIONS
HYDROGEN
HYDROGEN COMPOUNDS
HYDROGEN DEUTERIDE
HYDROGEN ISOTOPES
ISOTOPES
LIGHT NUCLEI
NONMETALS
NUCLEI
ODD-ODD NUCLEI
STABLE ISOTOPES
VIBRATIONAL STATES
WAVE FUNCTIONS