Covalency in metal-oxygen multiple bonds evaluated using oxygen K-edge spectroscopy and electronic structure theory

Stefan G Minasian; Jason M Keith; Enrique R Batista; Kevin S Boland; Joseph A Bradley; Scott R Daly; Stosh A Kozimor; Wayne W Lukens; Richard L Martin; Dennis Nordlund; Gerald T Seidler; David K Shuh; Dimosthenis Sokaras; Tolek Tyliszczak; Gregory L Wagner; Tsu-Chein Weng; Ping Yang

doi:10.1021/ja310223b

Journal article

Covalency in metal-oxygen multiple bonds evaluated using oxygen K-edge spectroscopy and electronic structure theory

Stefan G Minasian, Jason M Keith, Enrique R Batista, Kevin S Boland, Joseph A Bradley, Scott R Daly, Stosh A Kozimor, Wayne W Lukens, Richard L Martin, Dennis Nordlund, …

Journal of the American Chemical Society, Vol.135(5), pp.1864-1871

02/06/2013

DOI: 10.1021/ja310223b

PMID: 23351138

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Abstract

Advancing theories of how metal-oxygen bonding influences metal oxo properties can expose new avenues for innovation in materials science, catalysis, and biochemistry. Historically, spectroscopic analyses of the transition metal MO(4)(x-) anions have formed the basis for new M-O bonding theories. Herein, relative changes in M-O orbital mixing in MO(4)(2-) (M = Cr, Mo, W) and MO(4)(-) (M = Mn, Tc, Re) are evaluated for the first time by nonresonant inelastic X-ray scattering, X-ray absorption spectroscopy using fluorescence and transmission (via a scanning transmission X-ray microscope), and time-dependent density functional theory. The results suggest that moving from Group 6 to Group 7 or down the triads increases M-O e* (π*) mixing; for example, it more than doubles in ReO(4)(-) relative to CrO(4)(2-). Mixing in the t(2)* orbitals (σ* + π*) remains relatively constant within the same Group, but increases on moving from Group 6 to Group 7. These unexpected changes in orbital energy and composition for formally isoelectronic tetraoxometalates are evaluated in terms of periodic trends in d orbital energy and radial extension.

Microscopy, Electron, Scanning Transmission

X-Ray Absorption Spectroscopy

Quantum Theory

X-Rays

Oxygen - chemistry

Molecular Structure

Metals, Heavy - chemistry

Electrons

Details

Title: Subtitle: Covalency in metal-oxygen multiple bonds evaluated using oxygen K-edge spectroscopy and electronic structure theory
Creators: Stefan G Minasian - Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States
Jason M Keith
Enrique R Batista
Kevin S Boland
Joseph A Bradley - Lawrence Livermore National Laboratory
Scott R Daly
Stosh A Kozimor
Wayne W Lukens
Richard L Martin
Dennis Nordlund
Gerald T Seidler
David K Shuh
Dimosthenis Sokaras
Tolek Tyliszczak
Gregory L Wagner
Tsu-Chein Weng
Ping Yang
Resource Type: Journal article
Publication Details: Journal of the American Chemical Society, Vol.135(5), pp.1864-1871
DOI: 10.1021/ja310223b
PMID: 23351138
NLM abbreviation: J Am Chem Soc
ISSN: 1520-5126
eISSN: 1520-5126
Publisher: United States
Grant note: P41GM103393 / NIGMS NIH HHS P41 GM103393 / NIGMS NIH HHS P41RR001209 / NCRR NIH HHS P41 RR001209 / NCRR NIH HHS
Language: English
Date published: 02/06/2013
Academic Unit: Chemistry
Record Identifier: 9983985818102771

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