Jahn-Teller Effect on CF3I Photodissociation Dynamics.

Abstract

The Jahn-Teller (JT) effect, as a spontaneous symmetry-breaking mechanism arising from the coupling between electronic and nuclear degrees of freedom, is a widespread phenomenon in molecular and condensed matter systems. Here, we investigate the influence of the JT effect on the photodissociation dynamics of CF3I molecules. Based on ab initio calculation, we obtain the three-dimensional potential energy surfaces for 3Q0+ and 1Q1 states and establish a diabatic Hamiltonian model to study the wavepacket dynamics in the CF3I photodissociation process. Using the wave function of the final state after dissociation, we calculate the rotational density matrix of the CF3 fragment and analyze its rotational excitation under the JT effect, as well as its partial coherence property and selection rules. Our work paves the way to the experimental observation and quantification of the JT effect in molecular dissociation dynamics beyond the classical ball-and-stick model.