NEW POTENTIAL ENERGY SURFACES FOR THE ${\tilde X}$ AND ${\tilde A}$ STATES OF CH$_2^+$

Research Projects

Organizational Units

Journal Issue

Abstract

We report new {\textit{ab initio}} calculations of the three-dimensional potential energy surfaces for the Renner-effect coupled X~2A1 ground electronic state and A~2B1 first excited electronic state of the CH2+ molecule. We also make an {\textit{ab initio}} calculation of the spin-orbit coupling surface ASO(r12,r32,ρ) between these states. Using these {\it {ab initio}} surfaces, and our previously obtained}} {\bf{225},} 33-54 (1997).} {\textit{ab initio}} dipole moment and transition moment surfaces, in our computer program RENNER, we calculate term values and absorption line intensities. We compare with recently observed high resolution spectra. Adjusting two parameters in the potential surfaces we are able to achieve satisfactory agreement with the experimental results except for those that involve the A~ state (v2linear = 8, l = 1) vibronic level. The implication of this disagreement is discussed. Apart from having the facility of using dipole moment and transition moment surfaces so that absolute intensity calculations can be made, our RENNER computer program has the second unique feature of being able to calculate the energies of high lying rotational states because it is based on the Hougen-Bunker-Johns Hamiltonian. This has made it possible to study the phenomenon of rotational energy level clustering in Renner molecules. A recent study for PH2 exemplifies this aspect of our work}} {\bf{239,}} 160-173 (2006).}

Description

Author Institution: Steacie Institute for Molecular Sciences,; National Research Council of Canada, Ottawa,; Ontario K1A 0R6, Canada; Max-Planck-Institut f{u}r Astrophysik,; Karl-Schwarzschild-Strasse 1, Postfach 1523, D--85740 Garching, Germany; Max-Planck-Institut f{u}r Kohlenforschung,; Kaiser-Wilhelm-Platz 1, D--45470 M{u}lheim an der Ruhr, Germany; Department of Chemistry, The University of Chicago,; Chicago, Illinois 60637; Theoretische Chemie, Bergische Universitat,; D-42097 Wuppertal, Germany

Keywords

Citation