Sunahori Fumie X, Zhang Xiaopeng, Clouthier Dennis J
Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055, USA.
J Chem Phys. 2006 Aug 28;125(8):084310. doi: 10.1063/1.2338321.
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.
首次观测到了氢硫化铜（CuSH）的电子光谱。通过溅射的铜原子与H₂S或D₂S反应，在脉冲放电射流中生成了CuSH和CuSD。基于详细的转动分析以及与我们的CCSD(T)/6-311++G(3df,3pd)从头算计算预测结果的对应关系，在515 - 470 nm区域观测到的强激光诱导荧光带被归属为~A¹A″-X¹A′带系。激光诱导荧光和单振动能级发射光谱主要由Cu - S伸缩模式ν₃的短进展组成，这表明在电子激发时结构变化不大。利用CuSH的四种同位素异构体的转动常数确定了结合态的有效零点结构，即r″(CuS)=2.0916(3) Å，r″(SH)=1.364(3) Å，θ″ = 93.5(3)°，r′(CuS)=2.172(3) Å，r′(SH)=1.408(23) Å，以及θ′ = 93.5(24)°。对已知金属氢硫化物基态结构的比较表明，它们可被视为金属取代的硫化氢。对CuOH和CuSH的电子光谱及分子结构进行了比较和对比。
