Ab initio Study of Ground-State CS Photodissociation Via Highly Excited Electronic States

TL;DR

This study provides detailed ab initio calculations of CS photodissociation, revealing higher rates than previous estimates, which improves astrochemical modeling of sulfur-bearing molecules in interstellar environments.

Contribution

The paper introduces new high-accuracy ab initio potential energy curves and cross sections for CS photodissociation, significantly refining the rate calculations used in astrochemical models.

Findings

Photodissociation rate of CS is 2.9e-9 s^-1 under standard interstellar radiation.

The C-X (0-0) transition contributes 57% to the total photodissociation rate.

The calculated rate is three times higher than previous database values.

Abstract

Photodissociation by ultraviolet radiation is the key destruction pathway for CS in photon-dominated regions, such as diffuse clouds. However, the large uncertainties of photodissociation cross sections and rates of CS, resulting from a lack of both laboratory experiments and theoretical calculations, limit the accuracy of calculated abundances of S-bearing molecules by modern astrochemical models. Here we show a detailed \textit{ab initio} study of CS photodissociation. Accurate potential energy curves of CS electronic states were obtained by choosing an active space CAS(8,10) in MRCI+Q/aug-cc-pV(5+d)Z calculation with additional diffuse functions, with a focus on the \(B\) and \(C\,^1\Sigma^+\) states. Cross sections for both direct photodissociation and predissociation from the vibronic ground state were calculated by applying the coupled-channel method. We found that the \(C-X\) \((0-0)\) transition has extremely strong absorption due to a large transition dipole moment in the Franck-Condon region and the upper state is resonant with several triplet states via spin-orbit couplings, resulting in predissociation to the main atomic products C \((^3P)\) and S \((^1D)\). Our new calculations show the photodissociation rate under the standard interstellar radiation field is \(2.9\ee{-9}\)\,s\(^{-1}\), with a 57\% contribution from \(C-X\) \((0-0)\) transition. This value is larger than that adopted by the Leiden photodissociation and photoionization database by a factor of 3.0. Our accurate \textit{ab initio} calculations will allow more secure determination of S-bearing molecules in astrochemical models.

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