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Nitrogen Activation via Three-Coordinate Molybdenum Complexes: Comparison of Density Functional Theory Performance with Wave Function Based Methods

Citation

Graham, DC and Beran, GJO and Head-Gordon, M and Christian, G and Stranger, R and Yates, BF, Nitrogen Activation via Three-Coordinate Molybdenum Complexes: Comparison of Density Functional Theory Performance with Wave Function Based Methods, Journal of Physical Chemistry A, 109, (30) pp. 6762-6772. ISSN 1089-5639 (2005) [Refereed Article]

DOI: doi:10.1021/jp044217h

Abstract

Obtaining an accurate theoretical model for the activation of dinitrogen by three-coordinate molybdenum amide complexes (e.g. Mo(NH 2) 3) is difficult due to the interaction of various high- and low-spin open-shell complexes along the reaction coordinate which must be treated with comparable levels of accuracy in order to obtain reasonable potential energy surfaces. Density functional theory with present-day functionals is a popular choice in this situation; however, the dinitrogen activation reaction energetics vary substantially with the choice of functional. An assessment of the reaction using specialized wave function based methods indicates that although current density functionals in general agree qualitatively on the mechanistic details of the reaction, a variety of high-level electron correlation methods (including CCSD(T), OD(T), CCSD(2), KS-CCSD(T), and spin-flip CCSD) provide a consistent but slightly different representation of the system. © 2005 American Chemical Society.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Theoretical and Computational Chemistry
Research Field:Theoretical and Computational Chemistry not elsewhere classified
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Graham, DC (Dr David Graham)
Author:Yates, BF (Professor Brian Yates)
ID Code:36395
Year Published:2005
Web of Science® Times Cited:34
Deposited By:Chemistry
Deposited On:2005-08-01
Last Modified:2006-04-04
Downloads:0

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