### 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} E_{u} 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 1e_{u} molecular orbital of ethane produces the radical cation in the degenerate over(B, ∼)^{2} E_{u} electronic manifold, which is prone to the JT instability when distorted along the degenerate e_{g} 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} E_{u} electronic manifold of the radical cation is estimated to be ∼2.75 eV and ∼2.40 eV above its over(X, ∼)^{2} E_{g} and the over(A, ∼)^{2} A_{1 g} electronic states, respectively. The symmetry selection rule suggests PJT coupling of these electronic states along the vibrational modes of e_{g}/e_{u} symmetry. The quadratic JT spectrum simulated within the over(B, ∼)^{2} E_{u} 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} A_{1 g} - over(B, ∼)^{2} E_{u} 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} E_{g} - over(A, ∼)^{2} A_{1 g} - over(B, ∼)^{2} E_{u} PJT interactions in the theoretical model. Importance of the latter vibronic interactions is also discussed in the text.

Original language | English |
---|---|

Pages (from-to) | 76-89 |

Number of pages | 14 |

Journal | Chemical Physics |

Volume | 329 |

Issue number | 1-3 |

DOIs | |

Publication status | Published - 26 Oct 2006 |

Externally published | Yes |

### Fingerprint

### 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

*Chemical Physics*,

*329*(1-3), 76-89. https://doi.org/10.1016/j.chemphys.2006.06.001

**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.

Research output: Contribution to journal › Article

*Chemical Physics*, vol. 329, no. 1-3, pp. 76-89. https://doi.org/10.1016/j.chemphys.2006.06.001

}

TY - JOUR

T1 - Multistate and multimode vibronic dynamics

T2 - The Jahn-Teller and pseudo-Jahn-Teller effects in the ethane radical cation

AU - Kumar, R. R.

AU - Venkatesan, T. S.

AU - Mahapatra, S.

PY - 2006/10/26

Y1 - 2006/10/26

N2 - 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.

AB - 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.

KW - Conical intersections

KW - Ethane radical cation

KW - Jahn-Teller and pseudo-Jahn-Teller effects

KW - Nonadiabatic transitions

KW - Photoelectron spectroscopy

UR - http://www.scopus.com/inward/record.url?scp=33749506709&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33749506709&partnerID=8YFLogxK

U2 - 10.1016/j.chemphys.2006.06.001

DO - 10.1016/j.chemphys.2006.06.001

M3 - Article

AN - SCOPUS:33749506709

VL - 329

SP - 76

EP - 89

JO - Chemical Physics

JF - Chemical Physics

SN - 0301-0104

IS - 1-3

ER -