Density Functional Theory Study of the Multimode Jahn-Teller Effect - Ground State Distortion of Benzene Cation

Abstract

The multideterminental-DFT approach performed to analyze Jahn-Teller (JT) active molecules is described. Extension of this method for the analysis of the adiabatic potential energy surfaces and the multimode JT effect is presented. Conceptually a simple model, based on the analogy between the JT distortion and reaction coordinates gives further information about microscopic origin of the JT effect. Within the harmonic approximation the JT distortion can be expressed as a linear combination of all totally symmetric normal modes in the low symmetry minimum energy conformation, which allows calculating the Intrinsic Distortion Path, IDP, exactly from the high symmetry nuclear configuration to the low symmetry energy minimum. It is possible to quantify the contribution of different normal modes to the distortion, their energy contribution to the total stabilization energy and how their contribution changes along the IDP. It is noteworthy that the results obtained by both multideterminental-DFT and IDP methods for different classes of JT active molecules are consistent and in agreement with available theoretical and experimental values. As an example, detailed description of the ground state distortion of benzene cation is given.