title: The electronic spectrum of jet-cooled copper hydrosulfide (CuSH).
abstract: 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(2)S or D(2)S. Strong laser-induced fluorescence bands observed in the 515-470 nm region were assigned as the ~A (1)A"-X (1)A' 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 nu(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) degrees , r'(CuS)=2.172(3) A, r'(SH)=1.408(23) A, and theta'=93.5(24) degrees . 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.
authors.affiliation: Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055, USA.
authors.forename: Fumie X
authors.initials: FX
authors.lastname: Sunahori
authors.forename: Xiaopeng
authors.initials: X
authors.lastname: Zhang
authors.forename: Dennis J
authors.initials: DJ
authors.lastname: Clouthier
mesh_terms: D002627:Chemistry, Physical / Q000379:methods; D003300:Copper / Q000737:chemistry*; D004563:Electrochemistry / Q000379:methods*; D004581:Electronics; D004583:Electrons; D007834:Lasers; D008670:Metals; D008956:Models, Chemical; D008968:Molecular Conformation; D015394:Molecular Structure; D013050:Spectrometry, Fluorescence / Q000379:methods; D013053:Spectrophotometry; D013056:Spectrophotometry, Ultraviolet
chemical_list: D008670:Metals; D003300:Copper; C017846:cupric sulfide