Gaussian functions in Hylleraas-configuration interaction calculations: Potential curves for the e sup 3. Sigma. sup + sub u and the f sup 3. Sigma. sup + sub u states of hydrogen

Journal Article · Sun Apr 15 04:00:00 EDT 1990 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.457711· OSTI ID:6830090

Preiskorn, A; Lie, G C; Frye, D; Clementi, E ^[1]

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1. IBM Corporation, Department 48B/MS 428, Neighborhood Road, Kingston, New York 12401 (USA)

The explicitly correlated wave function method (Hylleraas-CI) with Cartesian Gaussian basis sets has been used to calculate the potential curve for the {ital e}{sup 3}{Sigma}{sup +}{sub {ital u}} and {ital f} {sup 3}{Sigma}{sup +}{sub {ital u}} states of the H{sub 2} molecule. Potential barriers of 215 and 10 300 cm{sup {minus}1} are predicted to exist in the {ital e}{sup 3}{Sigma}{sup +}{sub {ital u}} and {ital f} {sup 3}{Sigma}{sup +}{sub {ital u}} states, respectively, and their nature analyzed. Spectroscopic constants for H{sub 2} and D{sub 2} derived from the curves are compared with experiments and other theoretical calculations. It is concluded that the present potential curves are the best theoretical ones to-date and their accuracy is probably as good as the scanty experimental data. No {ital o}{sup 3}{Sigma}{sup +}{sub {ital u}} state below the {ital f} {sup 3}{Sigma}{sup +}{sub {ital u}} state is found in our calculations.

• OSTI ID: 6830090
• Journal Information: Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 92:8; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
CONFIGURATION INTERACTION
ELECTRONIC STRUCTURE
ELEMENTS
FUNCTIONS
HYDROGEN
MOLECULAR STRUCTURE
MOLECULES
NONMETALS
SPECTRAL FUNCTIONS
WAVE FUNCTIONS