A variationally computed room temperature line list for AsH${}_3$

Abstract

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${}^{-1}$.

Eq. (16) was corrected comparing to the published version

References in corpus (4)

• ExoMol line lists VII: The rotation-vibration spectrum of phosphine up to 1500 K
• Symmetry adapted ro-vibrational basis functions for variational nuclear motion calculations: TROVE approach
• General variational approach to nuclear-quadrupole coupling in rovibrational spectra of polyatomic molecules
• Tunnelling splitting in the phosphine molecule

Cited by in corpus (1)

• Use of the complete basis set limit for computing highly accurate ab initio dipole moments