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Title: Photoelectron imaging and theoretical study on the structure and chemical binding of the mixed-ligand M(I) complexes, [HMSH]{sup −} (M = Cu, Ag, and Au)

We have reported a combined photoelectron imaging and theoretical study on gaseous mixed-ligand M(I) complexes of [HMSH]{sup −} (M = Cu, Ag, and Au). With the aid of Franck-Condon simulations, vibrationally resolved photoelectron spectra yield accurate electron affinities of 3.269(6), 3.669(10), and 3.591(6) eV for [HCuSH], [HAgSH], and [HAuSH], respectively. And low-frequency modes are observed: 368(12) cm{sup −1} for [HCuSH], 286(12) cm{sup −1} for [HAgSH], and 327(12) cm{sup −1} for [HAuSH], respectively. Extensive theoretical calculations are performed to aid in the spectral assignments and the calculated values agree well with the experimental observations. Although the S and H atoms have little discrepancy in electronegativity (2.20 for H and 2.54 for S), distinct bonding properties are demonstrated between H–M and M–S bond. It is revealed that there exists significant ionic bonding between M–S in [HMSH]{sup −} (M = Cu, Ag, and Au), while a gradual transition from ionic behavior between H–Cu in [HCuSH]{sup −} to quite strong covalent bonding between H–Au in [HAuSH]{sup −}, supported by a variety of chemical bonding analyses.
Authors:
; ; ; ; ;  [1]
  1. State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)
Publication Date:
OSTI Identifier:
22253415
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 11; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AFFINITY; BONDING; CHEMICAL BONDS; ELECTRONEGATIVITY; LIGANDS; PHOTOELECTRON SPECTROSCOPY; SIMULATION