화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.112, No.36, 8215-8225, 2008
Complex dynamics at conical intersections: Vibronic spectra and ultrafast decay of electronically excited trifluoroacetonitrile radical cation
An ab initio quantum dynamical study is performed here to examine the complex nuclear motion underlying the first two photoelectron bands of trifluoroacetonitrile. The highly overlapping structures of the latter are found to originate from transitions to the five lowest electronic states (viz., (X) over tilde E-2, (A) over tilde (2)A(1), (B) over tilde (2)A(2), (C) over tilde (2)A(1), and (D) over tilde E-2 of the trifluoroacetonitrile radical cation. The Jahn-Teller (JT) instability of the doubly degenerate (X) over tilde and, (D) over tilde and their pseudo-Jahn-Teller (PJT) interactions with the nondegenerate (A) over tilde, (B) over tilde, and (C) over tilde electronic states along the degenerate vibrational modes lead to multiple multidimensional conical intersections and complex nuclear trajectories through them. It is found that the JT splitting is very weak in the (X) over tilde and relatively stronger in the (D) over tilde state. However, the PJT couplings play the pivotal role in the detailed shape of the vibronic bands of the radical cation. Ultrafasst nonradiative decay of electronically excited radical cation has been examined. The findings of this paper dire compared with the experimental data and are also discussed in relation to those observed for the methyl cyanide radical cation.