title: Photoelectron velocity-map imaging spectroscopic and theoretical study on the reactivity of the gold atom toward CH3SH, CH3OH, and H2O.
abstract: Photoelectron velocity-map imaging spectroscopy has been used to study the reaction of the anionic gold atom with the HR (R = SCH3, OCH3, OH) molecules. The solvated [Au···HR](-) and inserted [HAuR](-) products have been experimentally observed for R = SCH3, whereas only solvated [Au⋯HR](-) products were found for R = OCH3 and OH. This significant difference in the photoelectron spectra suggests the different reactivity of the Au(-) toward the CH3SH, CH3OH, and H2O molecules. Second order Møller-Plesset perturbation theory and coupled-cluster single double triple excitation calculations have been performed to aid the structural assignment of the spectra and to explore the reaction mechanism. Activation energies for the isomerizations of the solvated structures to the inserted ones in the Au(-)∕Au + HR reactions (R = OCH3 and OH) are predicted to be much higher than those for the Au(-)∕Au + CH3SH reactions, supporting the experimental observation. Theoretical calculations provide the evidence that the intriguing [HAuSCH3](-) product may be formed by the attachment of the electron onto the neutral HAuSCH3 species or the isomerization from the anionic [Au···HSCH3](-) one. These findings should be helpful for understanding the feature that the thiols are able to form the staple motifs, whereas CH3OH and H2O are not.
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
authors.forename: Zhengbo
authors.initials: Z
authors.lastname: Qin
authors.forename: Ran
authors.initials: R
authors.lastname: Cong
authors.forename: Xia
authors.initials: X
authors.lastname: Wu
authors.forename: Zhiling
authors.initials: Z
authors.lastname: Liu
authors.forename: Hua
authors.initials: H
authors.lastname: Xie
authors.forename: Zichao
authors.initials: Z
authors.lastname: Tang
authors.forename: Ling
authors.initials: L
authors.lastname: Jiang
authors.forename: Hongjun
authors.initials: H
authors.lastname: Fan
mesh_terms: D006046:Gold / Q000737:chemistry*; D000432:Methanol / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D056951:Photoelectron Spectroscopy; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D012997:Solvents; D013438:Sulfhydryl Compounds; D014867:Water; C005231:methylmercaptan; D006046:Gold; D000432:Methanol