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Degenerate four-wave mixing (DFWM) has been used to interrogate the nascent mercapto radicals (SH) emerging from photolysis of bulk-gas H 2 S samples at λ diss = 266 nm. These experiments reveal a cold non-Boltzmann distribution of SH molecules formed exclusively in vibrationless levels of the X 2 Π ground electronic state, with a non-thermal population...