Physical origins of high-order nonadiabatic molecular electric polarizabilities: Application to a twentieth-order perturbation study of H/sub 2/ /sup +/
It is demonstrated theoretically for arbitrary diatomic molecules (and atoms) and verified numerically with a twentieth-order perturbation study of the Stark effect for the ground state of H/sub 2/ /sup +/ that high-order nonadiabatic electric polarizabilities in each order result from the delicate partial balancing of larger opposing perturbational shifts in their kinetic, nuclear-potential, and field-potential components, where the relative magnitudes and signs of these component shifts can be precisely determined by general a priori relationships. This method of analysis, based upon a combination of the Stark virial, Hellmann-Feynman, and remainder theorems, and implemented via the perturbational-variational Rayleigh-Ritz formalism, provides a novel mechanism for studying in detail the physical origins of molecular polarizabilities.
- Research Organization:
- Department of Chemistry, University of Stirling, Stirling FK9 4LA, Scotland
- OSTI ID:
- 7104914
- Journal Information:
- Phys. Rev. A; (United States), Journal Name: Phys. Rev. A; (United States) Vol. 34:6; ISSN PLRAA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Rayleigh-Schroedinger perturbation theory at large order for radial Klein-Gordon equations
The virial theorem for the polarizable continuum model
Related Subjects
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
CATIONS
CHARGE DISTRIBUTION
CHARGED PARTICLES
DIPOLE MOMENTS
ELECTRIC DIPOLE MOMENTS
ELECTRIC FIELDS
ELECTRIC MOMENTS
ELECTRICAL PROPERTIES
HYDROGEN IONS
HYDROGEN IONS 2 PLUS
IONS
MOLECULAR IONS
PERTURBATION THEORY
PHYSICAL PROPERTIES
POLARIZABILITY
RITZ METHOD
STARK EFFECT