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Article
A Theoretical Study of ã⁴A₂ CH₂⁺
Journal of Molecular Spectroscopy (2002)
  • Per Jensen
  • Steven S Wesolowski
  • Nicole R. Brinkmann
  • Nancy A. Richardson
  • Yukio Yamaguchi
  • Henry F. Schaefer, University of Georgia
  • P R Bunker
Abstract
The potential energy surface and dipole moment surfaces of the ã4A2 electronic state of CH2+ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation–vibration term values for ã-state CH2+, CD+2, and CHD+ and to simulate the rotation and rotation–vibration absorption spectrum of CH2+ in the ã4A2 electronic state. Our work is motivated by studies of CH2+ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the /àground state pair, it turns out to be relatively high-lying, and we determine that Te(ã)=30447.5 cm−1. The equilibrium bond angle for ã-state CH2+ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic state.
Publication Date
February, 2002
DOI
10.1006/jmsp.2001.8503
Citation Information
Per Jensen, Steven S Wesolowski, Nicole R. Brinkmann, Nancy A. Richardson, et al.. "A Theoretical Study of ã⁴A₂ CH₂⁺" Journal of Molecular Spectroscopy Vol. 211 Iss. 2 (2002) p. 254 - 261
Available at: http://works.bepress.com/nancy_richardson/16/