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 ν1 and ν3 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.
@article{arxiv.1902.02281,
title = {A variationally computed room temperature line list for AsH$_{3}$},
author = {Phillip A. Coles and Sergei N. Yurchenko and Richard P. Kovacich and James Hobby and Jonathan Tennyson},
journal= {arXiv preprint arXiv:1902.02281},
year = {2019}
}
Comments
Eq. (16) was corrected comparing to the published version