Theoretical Modeling of Low-Energy Electronic Absorption Bands in Reduced Cobaloximes

Author(s)

Bhattacharjee, Anirban ^[1] ; Chavarot-Kerlidou, Murielle ^[2] ; Dempsey, Jillian L. ^{[3, 4]} ; Gray, Harry B. ^[3] ; Fujita, Etsuko ^[5] ; Muckerman, James T. ^[5] ; Fontecave, Marc ^{[2, 6]} ; Artero, Vincent ^[2] ; Arantes, Guilherme M. ^[7] ; Field, Martin J. ^[1]

Affiliation

^[1] Univ Grenoble 1, Inst Biol Struct Jean Pierre Ebel, DYNAMOP Grp, Dynamo Team, UMR 5075, CNRS, CEA, Grenoble 9 - France

^[2] Univ Grenoble 1, Lab Chim & Biol Met, UMR 5249, CNRS, CEA, DSV, RTSV, F-38054 Grenoble 9 - France

^[3] CALTECH, Beckman Inst, Pasadena, CA 91125 - USA

^[4] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 - USA

^[5] Brookhaven Natl Lab, Dept Chem, Upton, NY 11973 - USA

^[6] Coll France, F-75005 Paris - France

^[7] Univ Sao Paulo, Inst Quim, Dept Bioquim, BR-05508900 Sao Paulo - Brazil

• Document type: Journal article
• Source: ChemPhysChem; v. 15, n. 14, p. 2951-2958, OCT 6 2014.
• Web of Science Citations: 7

Abstract

The reduced Co-I states of cobaloximes are powerful nucleophiles that play an important role in the hydrogen-evolving catalytic activity of these species. In this work we analyze the low-energy electronic absorption bands of two cobaloxime systems experimentally and use a variety of density functional theory and molecular orbital ab initio quantum chemical approaches. Overall we find a reasonable qualitative understanding of the electronic excitation spectra of these compounds but show that obtaining quantitative results remains a challenging task. (AU)

• FAPESP's process: 12/02501-4 - Computer simulation and spectroscopic analysis of proteins involved in bioenergetics and in molecular recognition
• Grantee: Guilherme Menegon Arantes
• Support Opportunities: Regular Research Grants