Multimode Jahn-Teller and Pseudo-Jahn-Teller Interactions in the Cyclopropane Radical Cation: Complex Vibronic Spectra and Nonradiative Decay Dynamics
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- 作者：T. S. Venkatesan ; S. Mahapatra ; H.-D. Meyer ; H. Kö ; ppel ; L. S. Cederbaum
- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：March 15, 2007
- 年：2007
- 卷：111
- 期：10
- 页码：1746 - 1761
- 全文大小：240K
- 年卷期：v.111,no.10(March 15, 2007)
- ISSN：1520-5215
文摘
The complex vibronic spectra and the nonradiative decay dynamics of the cyclopropane radical cation (CP+)are simulated theoretically with the aid of a time-dependent wave packet propagation approach using themultireference time-dependent Hartree scheme. The theoretical results are compared with the experimentalphotoelectron spectrum of cyclopropane. The ground and first excited electronic states of CP+ are of 
2E'and Ã2E' ' type, respectively. Each of these degenerate electronic states undergoes Jahn-Teller (JT) splittingwhen the radical cation is distorted along the degenerate vibrational modes of e' symmetry. The JT splitcomponents of these two electronic states can also undergo pseudo-Jahn-Teller (PJT)-type crossings via thevibrational modes of e' ', 
and 
symmetries. These lead to the possibility of multiple multidimensionalconical intersections and highly nonadiabatic nuclear motions in these coupled manifolds of electronic states.In a previous publication [J. Phys. Chem. A 2004, 108, 2256], we investigated the JT interactions alone in the2E' ground electronic manifold of CP+. In the present work, the JT interactions in the Ã2E' ' electronicmanifold are treated, and our previous work is extended by considering the coupling between the 2E' andÃ2E' ' electronic states of CP+. The nuclear dynamics in this coupled manifold of two JT split doubly degenerateelectronic states is simulated by considering fourteen active and most relevant vibrational degrees of freedom.The vibronic level spectra and the ultrafast nonradiative decay of the excited cationic states are examinedand are related to the highly complex entanglement of electronic and nuclear degrees of freedom in thisprototypical molecular system.
2E'and Ã2E' ' type, respectively. Each of these degenerate electronic states undergoes Jahn-Teller (JT) splittingwhen the radical cation is distorted along the degenerate vibrational modes of e' symmetry. The JT splitcomponents of these two electronic states can also undergo pseudo-Jahn-Teller (PJT)-type crossings via thevibrational modes of e' ', and symmetries. These lead to the possibility of multiple multidimensionalconical intersections and highly nonadiabatic nuclear motions in these coupled manifolds of electronic states.In a previous publication [J. Phys. Chem. A 2004, 108, 2256], we investigated the JT interactions alone in the2E' ground electronic manifold of CP+. In the present work, the JT interactions in the Ã2E' ' electronicmanifold are treated, and our previous work is extended by considering the coupling between the 2E' andÃ2E' ' electronic states of CP+. The nuclear dynamics in this coupled manifold of two JT split doubly degenerateelectronic states is simulated by considering fourteen active and most relevant vibrational degrees of freedom.The vibronic level spectra and the ultrafast nonradiative decay of the excited cationic states are examinedand are related to the highly complex entanglement of electronic and nuclear degrees of freedom in thisprototypical molecular system.