화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.123, No.23, 4990-5004, 2019
First-Principles Calculation of Jahn-Teller Rotational Distortion Parameters
A theoretical and computational framework is presented for the parameters h(1) and h(2) that appear in the rotational Hamiltonian for molecules subject to the Jahn-Teller effect. Expressions that relate h(1) and h(2) to first and second moments of the degenerate normal coordinates as well as derivatives of the inertia tensor are presented in detail for both cylindrical and Cartesian coordinate systems. The method is demonstrated for three situations in which experimental information about h(1) (and/or h(2)) is available: the ground E-2(1)'' and E-2 states of the cyclopentadienyl (CsHs) and methoxy (CH3O) radicals, respectively, and the excited E-2 '' state of the nitrate (NO3) radical. Results for h(1) and h(2) parametrized by ab initio calculations exhibit good agreement with measured values, and they are demonstrably superior to those obtained with an approach based on first-order perturbation theory. The computational technology developed for h(1) and h(2) can be used to benchmark quantum chemistry calculations for molecules with Jahn-Teller effects and facilitate the analysis of their spectra.