The electronic spectrum of jet-cooled copper hydrosulfide(CuSH)

摘要

The electronic spectrum of copper hydrosulfide(CuSH)has been observed for the first time.CuSH and CuSD were produced in a pulsed discharge jet by the reaction of sputtered copper atoms with H_2S or D_2S.Strong laser-induced fluorescence bands observed in the 515-470 nm region were assigned as the A~1A"-X~1A'band system based on detailed rotational analysis and the correspondence with the predictions of our CCSD(T)/6-311++G(3df/,3pd)ab initio calculations.The laser-induced fluorescence and single vibronic level emission spectra consist primarily of a short progression in v_3,the Cu-S stretching mode,indicative of only modest structural changes on electronic excitation.The rotational constants of four isotopomers of CuSH were used to determine effective zero-point structures in the combining states as r"(CuS)=2.0916(3)A,r"(SH)=1.364(3)A,theta"=93.5(3)deg,r'(CuS)=2.172(3)A,r'(SH)=1.408(23)A,and thr'=93.5(24)deg.A comparison of the ground state structures of the known metal hydrosulfides shows that they can be considered to be metal-substituted hydrogen sulfides.The electronic spectra and molecular structures of CuOH and CuSH are compared and contrasted.