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Title: The X˜²B₁, ²B₂, ²A₁, and ²A₂ states of oxygen difluoride cation (F₂ O⁺) : high-level ab initio calculations and simulation of the ultraviolet photoelectron spectrum of F₂O
Authors: Wang, D
Chau, FT
Mok, DKW 
Lee, EPF
Beeching, L
Ogden, JS
Dyke, JM
Issue Date: 22-Jun-2001
Source: Journal of chemical physics, 22 June 2001, v. 114, no. 24, p. 10682-10694
Abstract: The ultraviolet photoelectron spectrum of F₂O was recorded with a higher resolution than previously published. New vibrational structure was observed in the second and third bands. Near state-of-the-art molecular orbital calculations were performed on the X˜¹ A₁ state of F₂O and the X˜²B₁ , ²B₂, ²A₁ , and ²A₂ state of F₂O⁺, and their potential energy functions were computed. Spectral simulations based on Franck–Condon factor calculations including the Duchinsky effect were carried out within the harmonic oscillator model and also with the inclusion of anharmonicity, in order to assist spectral assignment. Based on the computed ionization energies obtained with the coupled cluster and multireference configuration interaction methods with basis sets of up to quintuple zeta quality, the order of the low-lying cationic states of F₂O⁺ has been firmly established. However, the detailed assignment of the overlapping second and third photoelectron bands was only achieved with the aid of spectral simulation. The iterative Franck–Condon analysis (IFCA) procedure was carried out for the first band {F₂O⁺ (X˜²B₁) ← F₂O(X˜¹ A ₁ )} in the photoelectron spectrum. With the geometrical parameters of F₂O (X˜ ¹ A ₁ ) being fixed at the available experimental values, geometrical parameters of the X˜²B₁ state of F₂O⁺ were derived. Based on anharmonic Franck–Condon factor calculations, the recommended IFCA geometrical parameters for the ground state of F₂O⁺ are R(FO)=1.323±0.002Å and <FOF=107.3±0.2°.
Keywords: Fluorine compounds
Positive ions
Ab initio calculations
Ultraviolet photoelectron spectra
Orbital calculations
Potential energy functions
Franck-Condon factors
Harmonic oscillators
Iterative methods
Coupled cluster calculations
Configuration interactions
Publisher: American Institute of Physics
Journal: Journal of chemical physics 
ISSN: 0021-9606
EISSN: 1089-7690
DOI: 10.1063/1.1373690
Rights: © 2001 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in D.-C. Wang et al., J. Chem. Phys. 114, 10682 (2001) and may be found at http://link.aip.org/link/?jcp/114/10682.
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