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Theoretical investigation of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation

J. Chem. Phys. 118, 5880 (2003); doi:10.1063/1.1557191

Issue Date: 1 April 2003

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Clemens Woywod, Sandra Scharfe, Robert Krawczyk, and Wolfgang Domcke
Institute of Physical and Theoretical Chemistry, Technical University of Munich, D-85747 Garching, Germany

Horst Köppel
Institute of Physical Chemistry, University of Heidelberg, D-69120 Heidelberg, Germany
The spectroscopic and dynamic aspects of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation are investigated within an ab initio based vibronic-coupling model approach. Multireference second-order perturbation theory (CASPT2) has been employed to obtain the potential energies of the ground state and the first excited state of NH<sub>3</sub><sup>+</sup> as a function of symmetry-coordinate displacements. Vibronic-coupling parameters determining the Franck–Condon, Jahn–Teller, and pseudo-Jahn–Teller activity of the normal modes have been obtained from the ab initio data. The vibronic structures of the X-tilde 2A1 and à 2E photoelectron bands of ammonia have been calculated by numerical diagonalization of the vibronic Hamiltonian matrix. All six vibrational degrees of freedom are taken into account. The effects of Jahn–Teller and pseudo-Jahn–Teller interactions on the band shape of the à 2E photoelectron band are analyzed. The calculation of the time-dependent population probability of the à 2E state reveals a radiationless decay process on a time scale of 30 fs caused by a conical intersection of the X-tilde and à potential-energy surfaces, which arises from the combined effect of the Jahn–Teller splitting of the à 2E state and the X-tilde–à pseudo-Jahn–Teller interaction. In the X-tilde 2A1 band, the X-tilde–à pseudo-Jahn–Teller coupling results in the weak excitation of a single quantum of the degenerate bending mode. This theoretical result corroborates the earlier assignment of the vibronic structure of the X-tilde 2A1 photoelectron band of NH3 by Edvardsson et al. [J. Phys. B 32, 2583 (1999)]. ©2003 American Institute of Physics.
History: Received 6 November 2002; accepted 10 January 2003
Permalink: http://link.aip.org/link/?JCPSA6/118/5880/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.30.Gs
    Hyperfine interactions and isotope effects, Jahn–Teller effect in atoms and molecules
  • 31.15.Ar
    Ab initio calculations (atoms and molecules)
  • 33.20.Wr
    Vibronic, rovibronic, and rotation-electron-spin interactions (molecular spectra)
  • 33.50.-j
    Molecular fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion)
  • YEAR: 2003

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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