Cold collisions of SH− with He: Potential energy surface and rate coefficients
Résumé
Collisional energy transfer under cold conditions is of great importance from the fundamental and applicative point of view. Here, we investigate low temperature collisions of the SH− anion with He. We have generated a three-dimensional potential energy surface (PES) for the SH−(X1Σ+)–He(1S) van der Waals complex. The ab initio multi-dimensional interaction PES was computed using the explicitly correlated coupled cluster approach with simple, double, and perturbative triple excitation in conjunction with the augmented-correlation consistent-polarized valence triple zeta Gaussian basis set. The PES presents two minima located at linear geometries. Then, the PES was averaged over the ground vibrational wave function of the SH− molecule and the resulting two-dimensional PES was incorporated into exact quantum mechanical close coupling calculations to study the collisional excitation of SH− by He. We have computed inelastic cross sections among the 11 first rotational levels of SH− for energies up to 2500 cm−1. (De-)excitation rate coefficients were deduced for temperatures ranging from 1 to 300 K by thermally averaging the cross sections. We also performed calculations using the new PES for a fixed internuclear SH− distance. Both sets of results were found to be in reasonable agreement despite differences existing at low temperatures confirming that accurate predictions require the consideration of all internal degrees of freedom in the case of molecular hydrides. The rate coefficients presented here may be useful in interpreting future experimental work on the SH− negative ion colliding with He as those recently done for the OH−–He collisional system as well as for possible astrophysical applications in case SH− would be detected in the interstellar medium.
ACKNOWLEDGMENTS
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