Rovibrationally-Resolved Photodissociaton of SH${}^{+}$

Abstract

Photodissociation cross sections for the SH${}^{+}$ radical are computed from all rovibrational (RV) levels of the ground electronic state X${}^3{\Sigma }^{-}$ for wavelengths from threshold to 500~Å. The five electronic transitions, $2{}^3{\Sigma }^{-}\leftarrow$ X${}^3{\Sigma }^{-}$, $3{}^3{\Sigma }^{-}\leftarrow$ X${}^3{\Sigma }^{-}$, $A{}^3\Pi \leftarrow$ X${}^3{\Sigma }^{-}$, $2{}^3\Pi \leftarrow$ X${}^3{\Sigma }^{-}$, and $3{}^3\Pi \leftarrow$ X${}^3{\Sigma }^{-}$, are treated with a fully quantum-mechanical two-state model, {i.e. no non-adiabatic coupling between excited states was included in our work.}. The photodissociation calculations incorporate adiabatic potentials and transition dipole moment functions computed in the multireference configuration interaction approach along with the Davidson correction (MRCI+Q), but adjusted to match available experimental molecular data and asymptotic atomic limits. Local thermodynamic equilibrium (LTE) photodissociation cross sections were computed which assume a Boltzmann distribution of RV levels in the X${}^3{\Sigma }^{-}$ molecular state of the SH${}^{+}$ cation. The LTE cross sections are presented for temperatures in the range 1000-10,000~K. Applications of the current photodissociation cross sections to interstellar gas, photon-dominated regions, and stellar atmospheres are briefly discussed.

21 pages, 13 figures, 2 tables. Accepted in J Phys. B: At. Mol. Opt. Phys. for the special issue on Atomic and molecular data for astrophysics