On the perturbation of the [ital [tilde B]] [sup 2][ital A][prime] state of HCO by the 1 [sup 4][ital A][double prime] and 1 [sup 4][ital A][prime] states: Surfaces of intersection and spin--orbit interactions

Journal Article · Sat Jan 01 04:00:00 EST 1994 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.466962· OSTI ID:5285524

Manaa, M R; Yarkony, D R ^[1]

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1. Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218 (United States)

The excited [ital [tilde B]] [sup 2][ital A][prime] state of HCO is studied using multiconfiguration self-consistent field/configuration interaction wave functions of 300 000 to 1 400 000 terms. Equilibrium structures for the [ital [tilde X]] [sup 2][ital A][prime], [ital [tilde B]] [sup 2][ital A][prime], 1 [sup 4][ital A][double prime], and 1 [sup 4][ital A][prime] states are determined as is the [ital [tilde X]] [sup 2][ital A][prime]--[ital [tilde B]] [sup 2][ital A][prime] electronic transition dipole moment. This dipole transition moment vector is found to make an angle of [similar to]+34[degree] with the inertial [ital a] axis of the [ital [tilde B]] [sup 2][ital A][prime] state. The possibility of spin--orbit induced perturbation of the low-lying vibrational levels of the [ital [tilde B]] [sup 2][ital A][prime] state attributable to the 1 [sup 4][ital A][double prime] or 1 [sup 4][ital A][prime] states is considered. The minimum energy points on the surface of intersection of the [ital [tilde B]] [sup 2][ital A][prime] and 1 [sup 4][ital A][double prime] states, denoted MECP([ital [tilde B]] [sup 2][ital A][prime]--1 [sup 4][ital A][double prime]), and of the [ital [tilde B]] [sup 2][ital A][prime] and 1 [sup 4][ital A][prime] states, denoted MECP([ital [tilde B]] [sup 2][ital A][prime]--1 [sup 4][ital A][prime]), are determined. MECP([ital [tilde B]] [sup 2][ital A][prime]--1 [sup 4][ital A][double prime]) is located very close to the 1 [sup 4][ital A][double prime] equilibrium structure and is only [similar to]1500 cm[sup [minus]1] above the [ital [tilde B]] [sup 2][ital A][prime] minimum.

• DOE Contract Number: FG02-91ER14189
• OSTI ID: 5285524
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 100:1; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

664100* -- Theory of Electronic Structure of Atoms & Molecules-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ACYL RADICALS
CONFIGURATION INTERACTION
COUPLING
DIPOLE MOMENTS
DISTURBANCES
ENERGY LEVELS
EQUILIBRIUM
EXCITED STATES
FORMYL RADICALS
FUNCTIONS
INTERMEDIATE COUPLING
L-S COUPLING
RADICALS
STRUCTURE FACTORS
WAVE FUNCTIONS