Sulfur-33 Hyperfine Interactions in the Gas-Phase Electron Resonance Spectra of Π 2SH and Δ 1SO

Abstract

The gas‐phase electron resonance spectra of ${}^1{\Delta }^{33}\mathrm{SO}$ and ${}^2{\Pi }^{33}\mathrm{SH}$ have been observed in natural abundance. Since ³³S has a nuclear spin of $\frac{3}{2}$ , the observed spectra have rich magnetic hyperfine and electric quadrupole structure. This structure has been analyzed to determine the following magnetic hyperfine and quadrupole constants: for ${}^2{\Pi }^{33}\mathrm{SH}{\mathrm{—A}}_1\text{\hspace{0.17em}=\hspace{0.17em}71.1\hspace{0.17em}±\hspace{0.17em}1.0}\mathrm{MHz}{\mathrm{,\; e}}^2{q}_0\text{Q\hspace{0.17em}=\hspace{0.17em}13.5\hspace{0.17em}±\hspace{0.17em}2.0}\mathrm{MHz}$ ; for ${}^1{\Delta }^{33}\mathrm{SO}\text{—a\hspace{0.17em}=\hspace{0.17em}145.1\hspace{0.17em}±\hspace{0.17em}3.0}\mathrm{MHz}$ , where the symbols are defined in the text. The ${}^1{\Delta }^{33}\mathrm{SO}$ results are compared in a detailed way to similar hyperfine measurements in the ${}^3\Sigma$ ground state of ³³SO. The ${}^2{\Pi }^{33}\mathrm{SH}$ measurements are compared with the predictions of Hartree–Fock calculations on the ground state of SH.