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

TL;DR

This paper develops a spectroscopic model for nitric oxide's low-lying electronic states, combining empirical data and ab initio calculations to accurately predict its rovibronic structure for the near ultraviolet spectrum.

Contribution

It introduces a comprehensive method integrating empirical MARVEL data and ab initio calculations to model NO's electronic states, including complex avoided crossings.

Findings

Good agreement between calculated and observed energy levels

Validated the modeling approach for open shell systems

Provided detailed line lists for NO's ultraviolet spectrum

Abstract

The rovibronic structure of A$^2\Sigma^+$, B$^2\Pi$ and C$^2\Pi$ 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 the a combination of the empirical MARVEL procedure and ab initio calculations, and the available experimental data are critically evaluated. Abinito methods which deal simultaneously with the Rydberg-like A$^2\Sigma^+$ and C$^2\Pi$, and the valence B$^2\Pi$ state are tested. Methods of modeling the sharp avoided crossing between the B$^2\Pi$ and C$^2\Pi$ states are tested. A rovibronic Hamiltonian matrix is constructed using variational nuclear motion program DUO whose eigenvalues are fitted to the MARVEL energy levels. 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.