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.