Numerical and exact kinetic energy operator using Eckart conditions with one or several reference geometries: Application to HONO

Abstract

For the computation of rovibrational levels and their spectroscopic intensities, the Eckart conditions are essential to achieve the optimal separation between rotation and vibration. Dymarsky and Kudin [J. Chem. Phys. 122, 124103 (2005)] proposed a procedure for a simplified calculation of the Eckart rotation matrix. In the present work, we have adapted their approach to obtain a kinetic energy operator in curvilinear coordinates using a numerical but exact procedure without resorting to finite differences. Furthermore, we have modified this approach for the study of molecular systems with several minima, for which several Eckart reference geometries are required. The HONO molecular system has been used to show the efficiency of our implementation. Using the Eckart conditions with multi-reference geometries allows for a calculation of the rotational levels as well as frequencies and intensities of the infrared spectra of both HONO isomers with a single calculation