Enthalpy of Formation of ²Π_3/2 SH

The standard enthalpy of formation, Δ_fH°, of ²Π_3/2 SH has been determined at converged levels of ab initio electronic structure theory, including high-order coupled cluster and full configuration interaction benchmarks. The atomic Gaussian basis sets employed include the (aug)-cc-p(wC)VnZ family with n = 3, 4, 5, and 6. Extrapolations to the complete one-particle basis set and the full configuration interaction limits, where appropriate, have been performed to reduce remaining computational errors. Additional improvements in the enthalpy of formation of ²Π SH were achieved by appending the valence-only treatment with core−valence correlation, scalar relativistic and spin−orbit effects, and the diagonal Born−Oppenheimer correction. The recommended values for Δ_f and Δ_f of ²Π SH are and kJ mol^-1, respectively, corresponding to a recommended D_e = kJ mol^-1. The corresponding enthalpy of formation of ²Π SD is Δ_f = kJ mol^-1.