Probing the Electronic Structure and Chemical Bonding of Gold Oxides and Sulfides in AuOn- and AuSn- (n=1, 2)
- Washington State Univ., Richland, WA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Hmboldt Univ., Berlin (Germany)
The Au-O and Au-S interactions are essential in nanogold catalysis and nanotechnology, for which mono-gold oxide and sulfide clusters serve as the simplest molecular models. We report a combined photoelectron spectroscopy and ab initio study on AuO- and AuO2- and their valent isoelectronic AuS- and AuS2- species to probe their electronic structure and to elucidate the Au-O and Au-S chemical bonding. Vibrationally-resolved spectra were obtained at different photon energies, providing a wealth of electronic structure information for each species. Similar spectra were observed for AuO- and AuS- and for the linear OAuO- and SAuS- species. A bent isomer was also observed as Au(S2)- in the AuS2- spectra, whereas a similar Au(O2)- complex was not observed in the case of AuO2-. High-level ab initio calculations were conducted to aid spectral assignments and provide insight into the chemical bonding in the AuX- and AuX2- molecules. Excellent agreement is achieved between the calculated electronic excitations and the observed spectra. Configuration interactions and spin-orbit couplings were shown to be important and were necessary to achieve good agreement between theory and experiment. Strong covalent bonding was found in both the AuX- and the XAuX- species with multiple bonding characters. While Au(S2)- was found to be a low-lying isomer with a significant binding energy, Au(O2)- was shown to be unbound consistent with the experimental observation. The latter is understood in the context of the size-dependent reactivity of Aun- clusters with O2.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 949125
- Report Number(s):
- PNNL-SA-60420; JACSAT; 25396; KC0301020; TRN: US0901742
- Journal Information:
- Journal of the American Chemical Society, Vol. 130, Issue 28; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
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