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• W1999201905 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." @default.
• W1999201905 created "2016-06-24" @default.
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• W1999201905 date "2013-07-18" @default.
• W1999201905 modified "2023-09-26" @default.
• W1999201905 title "Photoelectron velocity-map imaging spectroscopic and theoretical study on the reactivity of the gold atom toward CH₃SH, CH₃OH, and H₂O" @default.
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• W1999201905 doi "https://doi.org/10.1063/1.4813631" @default.
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