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 04:00:00 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]

---

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), Journal Name: Journal of Chemical Physics; (United States) Vol. 99:1; 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
ANIONS
CHALCOGENIDES
CHARGED PARTICLES
CHLORINE COMPOUNDS
CHLORINE OXIDES
CONFIGURATION INTERACTION
ELECTRONIC EQUIPMENT
ENERGY
ENERGY LEVELS
EQUILIBRIUM
EQUIPMENT
EXCITED STATES
HALOGEN COMPOUNDS
HARMONIC OSCILLATORS
IONS
MOLECULAR IONS
OSCILLATORS
OXIDES
OXYGEN COMPOUNDS
POTENTIAL ENERGY
TWO-DIMENSIONAL CALCULATIONS