A variational theory for high Rydberg Stark ionization threshold scaling laws in atomic hydrogen

Journal Article · Mon Nov 01 04:00:00 EST 1976 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.433583· OSTI ID:7346822

Herrick, D R

We examine hydrogen atom Stark energies calculated with nonlinear variational theory using square-integrable wavefunctions. The trial function for each state has a characteristic critical field (F*) above which the variational energy is complex. F* approximates the experimentally important Stark ionization threshold for Rydberg states and typifies critical fields encountered in mathematical ''catastrophe theory.'' Zero-field wavefunctions yield analytic formulas for both threshold fields and energies in terms of parabolic quantum numbers. Aspects of the model suggest a ''law of corresponding states'' for Stark ionization near the critical field. The threshold fields scale as n/sup -4/ for all high Rydberg Stark states, while threshold energies scale as n/sup -2/ for the most unstable Stark components, and as n/sup -8///sup 3/ for the most stable components. This variationally determined threshold behavior is compared with existing classical ionization criteria, perturbation theory, and semiclassical threshold orderings for different Stark components. (AIP)

• Research Organization: Chemistry Department and Institute of Theoretical Science, University of Oregon, Eugene, Oregon 97403
• OSTI ID: 7346822
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 65:9; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
CRYOGENIC FLUIDS
ELEMENTS
FLUIDS
FUNCTIONS
HYDROGEN
IONIZATION POTENTIAL
NONMETALS
STARK EFFECT
VARIATIONAL METHODS
WAVE FUNCTIONS