A spectroscopic model for the low-lying electronic states of NO

Qianwei Qu; Bridgette Cooper; Sergei N Yurchenko; Jonathan Tennyson

doi:10.1063/5.0038527

A spectroscopic model for the low-lying electronic states of NO

J Chem Phys. 2021 Feb 21;154(7):074112. doi: 10.1063/5.0038527.

Authors

Qianwei Qu¹, Bridgette Cooper¹, Sergei N Yurchenko¹, Jonathan Tennyson¹

Affiliation

¹ Department of Physics and Astronomy, University College London, London WC1E 6BT, United Kingdom.

PMID: 33607908
DOI: 10.1063/5.0038527

Abstract

The rovibronic structure of A²Σ⁺, B²Π, and C²Π states of nitric oxide (NO) is studied with the aim of producing comprehensive line lists for its near ultraviolet spectrum. Empirical energy levels for the three electronic states are determined using a combination of the empirical measured active rotation-vibration energy level (MARVEL) procedure and ab initio calculations, and the available experimental data are critically evaluated. Ab initio methods that deal simultaneously with the Rydberg-like A²Σ⁺ and C²Π and the valence B²Π state are tested. Methods of modeling the sharp avoided crossing between the B²Π and C²Π states are tested. A rovibronic Hamiltonian matrix is constructed using the variational nuclear motion program Duo whose eigenvalues are fitted to the MARVEL. The matrix also includes coupling terms obtained from the refinement of the ab initio potential energy and spin-orbit coupling curves. Calculated and observed energy levels agree well with each other, validating the applicability of our method and providing a useful model for this open shell system.