Collisional excitation of propyne (CH$_3$CCH) by He atoms

Abstract

A detailed interpretation of the detected emission lines of environments in which propyne (or methyl acetylene, CH$_3$CCH) is observed requires a knowledge of its collisional rate coefficients with the most abundant species in the interstellar medium, He or H$_2$. We present the first three-dimensional potential energy surface (3D-PES) for the CH$_3$CCH-He molecular complex, study the dynamics of the collision, and report the first set of rate coefficients for temperatures up to 100 K for the collisional excitation of the lowest 60 ortho rotational levels and 60 para rotational levels of CH$_3$CCH by He atoms. We computed the 3D-PES with the explicitly correlated coupled-cluster with single-, double-, and perturbative triple-excitation method, in conjunction with the augmented correlation-consistent triple zeta basis set (CCSD(T)-F12a/aug-cc-pVTZ). The 3D-PES was fitted to an analytical function. Scattering computations of pure rotational (de-)excitation of CH$_3$CCH by collision with He atoms were performed and the state-to-state cross sections were computed using the close coupling method for total energies up to 100 cm$^{-1}$ and with the coupled states approximation at higher energy for both ortho and para symmetries of CH$_3$CCH. The PES obtained is caracterized by a large anisotropy and a potential well depth of 51.04 cm$^{-1}$. By thermally averaging the collisional cross sections, we determined quenching rate coefficients for kinetic temperatures up to 100 K. A strong even $Δj$ propensity rule at almost all collision energies exists for CH$_3$CCH-He complex. To evaluate the impact of rate coefficients in the analysis of observations, we carried out non-LTE radiative transfer computations of the excitation temperatures and we demonstrate that LTE conditions are typically not fulfilled for the propyne molecule.