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Title: On The Chemical Bonding of Gold In Auro-Boron Oxide Clusters AunBO-(n=1-3)

Abstract

During experiment on Au-B alloy clusters, an auro-boron oxide cluster Au2BO- was observed to be an intense peak dominating the Au-B mass spectra, along with weaker signals for AuBO- and Au3BO-. Well-resolved photoelectron spectra have been obtained for the three new oxide clusters, which exhibit an odd-even effect in their electron binding energies. Au2BO- is shown to be a closed shell molecule with a very high electron binding energy, whereas AuBO and Au3BO neutrals are shown to be closed shell species with large HOMO-LUMO gaps, resulting in relatively low electron affinities. Density functional calculations were performed for both AunBO- (n = 1-3) and the corresponding HnBO- species in order to evaluate the analogy in bonding between gold and hydrogen in B-Au clusters. The combination of experiment and theory allowed us to establish the structures and chemical bonding of these tertiary clusters. We find that the first gold atom does mimic hydrogen and interacts with the BO unit to produce a linear AuBO- structure. This unit preserves its identity when interacting with additional gold atoms: a linear Au-[AuBO] complex is formed when adding one extra Au atom and two isomeric Au2-[AuBO] complexes are formed when adding two extra Au atoms. Sincemore » BO- is isoelectronic to CO, the AunBO- species can be alternatively viewed as Aun interacting with a BO- unit. The structures and chemical bonding in AunBO- are compared to those in the corresponding AunCO complexes.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
901183
Report Number(s):
PNNL-SA-52441
17812; KP1303000; TRN: US200713%%157
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry A, 111(9):1648-1658; Journal Volume: 111; Journal Issue: 9
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; ALLOYS; ATOMS; BINDING ENERGY; BONDING; ELECTRONS; FUNCTIONALS; GOLD; HYDROGEN; MASS SPECTRA; OXIDES; SPECTRA; Environmental Molecular Sciences Laboratory

Citation Formats

Zubarev, Dmitry Y., Boldyrev, Alexander I., Li, Jun, Zhai, Hua-jin, and Wang, Lai S.. On The Chemical Bonding of Gold In Auro-Boron Oxide Clusters AunBO-(n=1-3). United States: N. p., 2007. Web. doi:10.1021/jp0657437.
Zubarev, Dmitry Y., Boldyrev, Alexander I., Li, Jun, Zhai, Hua-jin, & Wang, Lai S.. On The Chemical Bonding of Gold In Auro-Boron Oxide Clusters AunBO-(n=1-3). United States. doi:10.1021/jp0657437.
Zubarev, Dmitry Y., Boldyrev, Alexander I., Li, Jun, Zhai, Hua-jin, and Wang, Lai S.. Wed . "On The Chemical Bonding of Gold In Auro-Boron Oxide Clusters AunBO-(n=1-3)". United States. doi:10.1021/jp0657437.
@article{osti_901183,
title = {On The Chemical Bonding of Gold In Auro-Boron Oxide Clusters AunBO-(n=1-3)},
author = {Zubarev, Dmitry Y. and Boldyrev, Alexander I. and Li, Jun and Zhai, Hua-jin and Wang, Lai S.},
abstractNote = {During experiment on Au-B alloy clusters, an auro-boron oxide cluster Au2BO- was observed to be an intense peak dominating the Au-B mass spectra, along with weaker signals for AuBO- and Au3BO-. Well-resolved photoelectron spectra have been obtained for the three new oxide clusters, which exhibit an odd-even effect in their electron binding energies. Au2BO- is shown to be a closed shell molecule with a very high electron binding energy, whereas AuBO and Au3BO neutrals are shown to be closed shell species with large HOMO-LUMO gaps, resulting in relatively low electron affinities. Density functional calculations were performed for both AunBO- (n = 1-3) and the corresponding HnBO- species in order to evaluate the analogy in bonding between gold and hydrogen in B-Au clusters. The combination of experiment and theory allowed us to establish the structures and chemical bonding of these tertiary clusters. We find that the first gold atom does mimic hydrogen and interacts with the BO unit to produce a linear AuBO- structure. This unit preserves its identity when interacting with additional gold atoms: a linear Au-[AuBO] complex is formed when adding one extra Au atom and two isomeric Au2-[AuBO] complexes are formed when adding two extra Au atoms. Since BO- is isoelectronic to CO, the AunBO- species can be alternatively viewed as Aun interacting with a BO- unit. The structures and chemical bonding in AunBO- are compared to those in the corresponding AunCO complexes.},
doi = {10.1021/jp0657437},
journal = {Journal of Physical Chemistry A, 111(9):1648-1658},
number = 9,
volume = 111,
place = {United States},
year = {Wed Feb 14 00:00:00 EST 2007},
month = {Wed Feb 14 00:00:00 EST 2007}
}
  • We report a combined photoelectron spectroscopy (PES) and density functional theory (DFT) study on a series of tritantalum oxide clusters, Ta3On-. Well-resolved PES spectra are obtained for Ta3On- (n = 1-8) at several detachment photon energies, yielding electronic structure information which is used for comparison with the DFT calculations. A trend of sequential oxidation is observed as a function of O content until Ta3O8-, which is a stoichiometric cluster. Extensive DFT calculations are performed in search of the lowest energy structures for both the anions and neutrals. The first three O atoms are shown to successively occupy the bridging sitesmore » in the Ta3 triangle. The next three O atoms each occupy a terminal site, with the seventh and eighth O atoms forming a double-bridge and a double-terminal, respectively. The Ta3O7- anion is found to possess a localized electron pair on a single Ta center, making it an interesting molecular model for Ta3+ surface sites. Molecular orbital analyses are performed to elucidate the chemical bonding in the Ta3On- clusters.« less
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