A multireference configuration interaction study of the low-lying electronic states of ClO[sub 2][sup +] and the [ital X] [sup 1][ital A][sub 1] state of ClO[sub 2][sup [minus]]

Journal Article · Thu Jul 01 00:00:00 EDT 1993 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.465808· OSTI ID:6368835

Peterson, K A ^[1]; Werner, H ^[2]

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1. Molecular Science Research Center, Pacific Northwest Laboratory, Richland, Washington 99352 (United States)
2. Fakultaet fuer Chemie, Universitaet Bielefeld, 4800 Bielefeld (Germany)

Near-equilibrium two-dimensional ([ital C][sub 2][ital v] symmetry) potential energy functions of the first seven electronic states of ClO[sub 2][sup +] and the ground [ital X] [sup 1][ital A][sub 1] electronic state of ClO[sub 2][sup [minus]] have been calculated using internally contracted multireference configuration interaction (CMRCI) wave functions. In the case of ClO[sub 2][sup +], five electronic states ([sup 3][ital B][sub 2], [sup 3][ital A][sub 2], [sup 1][ital A][sub 2], [sup 3][ital B][sub 1], and [sup 1][ital B][sub 1]) are predicted to lie within 3 eV of the [ital X] [sup 1][ital A][sub 1] ground state, while a [sup 1][ital B][sub 2] state has a calculated [ital T][sub [ital e]] of just over 5 eV. In the [ital X] state, the equilibrium geometry is calculated by CMRCI to be [ital r][sub [ital e]]=1.423 A and [theta][sub [ital e]]=120.8[degree]. Harmonic vibrational frequencies of 1012 ([omega][sub 1]), 511 ([omega][sub 2]), and 1283 cm[sup [minus]1] ([omega][sub 3]) were derived from the computed potential energy function, and [omega][sub 1] and [omega][sub 2] were found to be in good agreement with the values estimated from the photoelectron spectrum of ClO[sub 2]. For the [ital X] [sup 1][ital A][sub 1] state of ClO[sub 2][sup [minus]], calculated spectroscopic constants include [ital r][sub [ital e]]=1.573 A, [theta][sub [ital e]]=113.9[degree], [omega][sub 1]=789 cm[sup [minus]1], [omega][sub 2]=378 cm[sup [minus]1], and [omega][sub 3]=848 cm[sup [minus]1]. Electric dipole moment functions have also been derived for both species in their electronic ground states. The calculated equilibrium dipole moments for ClO[sub 2][sup +] and ClO[sub 2][sup [minus]] 1.46 and 2.55 D, respectively, make them good candidates for observation by pure rotational spectroscopy.

• DOE Contract Number: FG06-89ER75522; AC06-76RL01830
• OSTI ID: 6368835
• Journal Information: Journal of Chemical Physics; (United States), Vol. 99:1; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
CHLORINE OXIDES
EXCITED STATES
MOLECULAR IONS
ANIONS
CONFIGURATION INTERACTION
EQUILIBRIUM
HARMONIC OSCILLATORS
POTENTIAL ENERGY
TWO-DIMENSIONAL CALCULATIONS
CHALCOGENIDES
CHARGED PARTICLES
CHLORINE COMPOUNDS
ELECTRONIC EQUIPMENT
ENERGY
ENERGY LEVELS
EQUIPMENT
HALOGEN COMPOUNDS
IONS
OSCILLATORS
OXIDES
OXYGEN COMPOUNDS
664100* - Theory of Electronic Structure of Atoms & Molecules- (1992-)