High-Temperature Line List of Phosphaethyne (HCP).

Abstract

Phosphaethyne (HCP) has been detected in circumstellar envelopes; its spectroscopic line list is helpful for modeling the relevant atmospheric opacity. We present the first comprehensive line list for HCP(X1Σ+) using robust first-principles methods. The analytical potential energy surface and dipole moment surface were constructed based on 26478 ab initio points from coupled-cluster calculations, along with the considerations of core-valence electron correlation and scalar relativistic effects. The variational nuclear motion program TROVE was used to obtain the ro-vibrational energy levels, Einstein A coefficients, and so on. The J-dependent Coriolis-decoupled Hamiltonian was adopted in the variational calculations with k ≤ 20, and the linear molecule treatment was applied to consider the l-type doubling of the bending vibration. The line list contains almost 0.45 billion transitions between 1.21 million levels with rotational excitation up to J = 200. It covers the wavenumber range of 0-9000 cm-1 (wavelengths above 1.11 μm) and is suitable for temperatures up to 3000 K. The millimeter wave spectra agree well with the experiments, and the Fermi resonance between 2v2 and v3 bands has been reproduced.