PUB - Publikationen an der Universität Bielefeld

A new full-dimensional (6D) diabatic potential energy surface (PES) model is presented representing the five lowest PESs corresponding to the X(2)A '(2), A(2)E", and (BE)-E-2 ' electronic states of the nitrate radical (NO3). It is based on high-level ab initio calculations of roughly 90000 energy data over a wide range of nuclear configurations and represents the energies with a root mean-squares (rms) error of about 100 cm (1). An accurate dipole surface was developed for the X state as well. The new PES model is used to re-investigate the infra-red (IR) spectrum corresponding to the electronic ground state by full dimensional quantum dynamics simulations. Vibrational eigenstates, IR transition probabilities, and isotopic shifts are computed and analyzed. Levels up to 2000 cm (1) are obtained and show good to excellent agreement with known experimental values. Some larger deviations are observed and discussed as well. The new results are in agreement with previous theoretical studies that the disputed nu(3) fundamental corresponds to a frequency of roughly 1022 cm (1) and that the prominent experimental feature observed at 1492 cm (1) is due to the 3(1)4(1) (e ') combination mode. Observed discrepancies in the IR intensities may be explained by coupling to the B state which is also analysed by diabatic decomposition of the eigenstates. (C) 2018 Elsevier B.V. All rights reserved.