Multistate and multimode vibronic dynamics

The Jahn-Teller and pseudo-Jahn-Teller effects in the ethane radical cation

R. R. Kumar, T. S. Venkatesan, S. Mahapatra

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Multimode Jahn-Teller (JT) and pseudo-Jahn-Teller (PJT) coupling effects in the photoelectron spectrum of ethane are theoretically investigated. In this article, we focus on the vibronic structure of the second excited over(B, ∼)2 Eu electronic manifold of the ethane radical cation which reveals an asymmetric band in the 14.5-16.5 eV ionization energy range in the experimental recordings. Ionization of an electron from the third occupied 1eu molecular orbital of ethane produces the radical cation in the degenerate over(B, ∼)2 Eu electronic manifold, which is prone to the JT instability when distorted along the degenerate eg vibrational modes. The theoretical formalism employed here is based on a model diabatic Hamiltonian and a quadratic vibronic coupling scheme with the parameters derived from ab initio electronic structure calculations. The photoelectron band is calculated by carrying out quantum dynamical simulations in the coupled manifold of electronic states. The over(B, ∼)2 Eu electronic manifold of the radical cation is estimated to be ∼2.75 eV and ∼2.40 eV above its over(X, ∼)2 Eg and the over(A, ∼)2 A1 g electronic states, respectively. The symmetry selection rule suggests PJT coupling of these electronic states along the vibrational modes of eg/eu symmetry. The quadratic JT spectrum simulated within the over(B, ∼)2 Eu electronic manifold shows two maxima at ∼ 14.96 eV and ∼15.76 eV which are attributed to the two JT split adiabatic sheets of this electronic manifold. This is in good accord with their position observed at ∼15.0 eV and ∼15.8 eV, respectively, in the experimental recording. The diffuse structure of the overall band can be accounted to a large extent by considering the over(A, ∼)2 A1 g - over(B, ∼)2 Eu PJT interactions. The overall shape of the theoretical band agrees very well with the experimental results. Further refinement of the theoretical results may be accomplished by including over(X, ∼)2 Eg - over(A, ∼)2 A1 g - over(B, ∼)2 Eu PJT interactions in the theoretical model. Importance of the latter vibronic interactions is also discussed in the text.

Original languageEnglish
Pages (from-to)76-89
Number of pages14
JournalChemical Physics
Volume329
Issue number1-3
DOIs
Publication statusPublished - 26 Oct 2006
Externally publishedYes

Fingerprint

Jahn-Teller effect
Ethane
Electronic states
ethane
Cations
Photoelectrons
cations
electronics
Hamiltonians
Ionization potential
Molecular orbitals
Ionization
Electronic structure
vibration mode
photoelectrons
Electrons
recording
ionization
interactions
symmetry

Keywords

  • Conical intersections
  • Ethane radical cation
  • Jahn-Teller and pseudo-Jahn-Teller effects
  • Nonadiabatic transitions
  • Photoelectron spectroscopy

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Multistate and multimode vibronic dynamics : The Jahn-Teller and pseudo-Jahn-Teller effects in the ethane radical cation. / Kumar, R. R.; Venkatesan, T. S.; Mahapatra, S.

In: Chemical Physics, Vol. 329, No. 1-3, 26.10.2006, p. 76-89.

Research output: Contribution to journalArticle

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KW - Nonadiabatic transitions

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