Rovibronic spectroscopy of PN from first principles

• Published in: arXiv.org 2021-11
• Main Authors: Semenov, Mikhail, El-Kork, Nayla, Yurchenko, Sergei N, Tennyson, Jonathan
• Format: Article
• Language: English
• Subjects: Absorption spectra; Angular momentum; Dipole moments; Electric dipoles; Electron spin; Electron states; Electronic structure; First principles; Mathematical analysis; Potential energy; Spectrum analysis; Spin-orbit interactions
• ISSN: 2331-8422
• DOI: 10.48550/arxiv.2111.05107

We report an ab initio study on the rovibronic spectroscopy of the closed-shell diatomic molecule phosphorous mononitride, PN. The study considers the nine lowest electronic states, \(X\,{}^{1}\Sigma^{+}\), \(A\,{}^{1}\Pi\), \(C\,{}^{1}\Sigma^{-}\), \(D\,{}^{1}\Delta\), \(E\,{}^{1}\Sigma^{-}\), \(a\,{}^{3}\Sigma^{+}\), \(b\,{}^{3}\Pi\), \(d\,{}^{3}\Delta\) and \(e\,{}^{3}\Sigma^{-}\) using high level electronic structure theory and accurate nuclear motion calculations. The ab initio data cover 9 potential energy, 14 spin-orbit coupling, 7 electronic angular momentum coupling, 9 electric dipole moment and 8 transition dipole moment curves. The Duo nuclear motion program is used to solve the coupled nuclear motion Schr\"{o}dinger equations for these nine electronic states and to simulate rovibronic absorption spectra of \(^{31}\)P\(^{14}\)N for different temperatures, which are compared to available spectroscopic studies. Lifetimes for all states are calculated and compared to previous results from the literature. The calculated lifetime of the \(A\,{}^{1}\Pi\) state shows good agreement with an experimental value from the literature, which is an important quality indicator for the ab initio \(A\)-\(X\) transition dipole moment.