A variationally computed room temperature line list for AsH\(_{3}\)

• Published in: arXiv.org
• Main Authors: Coles, Phillip A, Yurchenko, Sergei N, Kovacich, Richard P, Hobby, James, Tennyson, Jonathan
• Format: Paper Journal Article
• Language: English
• Published: Ithaca Cornell University Library, arXiv.org 06.02.2019
• Subjects: Absorption cross sections; Computation; Dipole moments; Electronic structure; Energy levels; Mathematical analysis; Physics - Chemical Physics; Physics - Earth and Planetary Astrophysics; Potential energy; Room temperature; Surface chemistry; Wavelengths
• ISSN: 2331-8422
• DOI: 10.48550/arxiv.1902.02281

Calculations are reported on the rotation-vibration energy levels of the arsine molecule with associated transition intensities. A potential energy surface (PES) obtained from \textit{ab initio} electronic structure calculations is refined to experimental data, and the resulting energy levels display sub-wavenumber accuracy for all reliably known \(J=0\) term values under 6500 cm\(^{-1}\). After a small empirical adjustment of the band centres, our calculated (\(J=1-6\)) rovibrational states reproduce 578 experimentally derived energies with a root-mean-square error of 0.122 cm\(^{-1}\). Absolute line intensities are computed using the refined PES and a new dipole moment surface (DMS) for transitions between states with energies up to 10~500 cm\(^{-1}\) and rotational quantum number \(J=30\). The computed DMS reproduces experimental line intensities to within 10\% uncertainty for the \(\nu_1\) and \(\nu_3\) bands. Furthermore, our calculated absorption cross-sections display good agreement with the main absorption features recorded in Pacific Northwest National Laboratory (PNNL) for the complete range of \(600-6500\) cm\(^{-1}\).