Adiabatic correction for nonlinear triatomic molecules: Techniques and calculations

Journal Article · Wed Mar 15 04:00:00 EST 1978 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.436104· OSTI ID:5034462

Bardo, R D; Wolfsberg, M

In the Born-Oppenheimer (BO) approximation the isotopic-mass-independent BO electronic energy is the potential energy surface for nuclear motion. The first correction to the BO approximation is obtained by adding the isotopic-mass-dependent adiabatic correction C to this potential energy surface. The adiabatic correction for a nonlinear triatomic molecule in a nondegenerate electronic state is expressed in terms of one-electron integrals over atomic basis functions. Both single determinant molecular orbital BO electronic wavefunctions and configuration interaction wavefunctions are discussed. The adiabatic correction is calculated for H/sub 2/O and H/sup +//sub 3/ and their isotopic variants at the respective equilibrium internuclear geometries. Theses adiabatic corrections are combined with those previously calculated for diatomic molecules to obtain correction factors to equilibrium constants for H/D isotopic exchange reactions calculated within the framework of the BO approximation.

• Research Organization: Department of Chemistry, University of California, Irvine, California 92717
• OSTI ID: 5034462
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 68:6; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400203 -- Isotope Exchange & Isotope Separation-- (-1987)
640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ADIABATIC APPROXIMATION
BORN-OPPENHEIMER APPROXIMATION
CATIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
DEUTERIUM
ELECTRONIC STRUCTURE
EQUILIBRIUM
HYDROGEN COMPOUNDS
HYDROGEN IONS
HYDROGEN IONS 3 PLUS
HYDROGEN ISOTOPES
IONS
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LIGHT NUCLEI
MOLECULAR IONS
NUCLEI
ODD-ODD NUCLEI
OXYGEN COMPOUNDS
REACTION KINETICS
STABLE ISOTOPES
WATER