Activation of Carbon-Hydrogen and Hydrogen-Hydrogen Bonds by Copper-Nitrenes: A Comparison of Density Functionality Theory with Single- and Multireference Correlation Consistent Composite Approaches

Description:

Article on a comparison of density functional theory with single- and multireference correlation consistent composite approaches (ccCA).

Creator(s):
Creation Date: October 19, 2009
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
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Total Uses: 189
Past 30 days: 6
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Creator (Author):
Tekarli, Sammer M.

University of North Texas

Creator (Author):
Williams, T. Gavin

University of North Texas

Creator (Author):
Cundari, Thomas R., 1964-

University of North Texas

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
Date(s):
  • Creation: October 19, 2009
Description:

Article on a comparison of density functional theory with single- and multireference correlation consistent composite approaches (ccCA).

Degree:
Department: Chemistry
Note:

Reprinted with permission from the Journal of Chemical Theory and Computation. Copyright 2009 American Chemical Society.

Note:

Abstract: The kinetics and thermodynamics of copper-mediated nitrene insertion into C-H and H-H bonds (the former of methane) have been studied using several levels of theory: B3LYP/6-311++G(d,p), B97-1/cc-pVTZ, PBE1KCIS/cc-pVTZ, and ccCA (correlation consistent Composite Approach). The results show no significant difference among the DFT methods. All three DFT methods predict the ground state of the copper-nitrene model complex, L'Cu(NH), to be a triplet, while single reference ccCA predicts the singlet to be the ground state. The contributions to the total ccCA energy indicate that the singlet state is favored at the MP2/CBS level of theory, while electron correlation beyond this level (CCSD(T)) favors a triplet state, resulting in a close energetic balance between the two states. A multireference ccCA method is applied to the nitrene active species and supports the assignment of a singlet ground state. In general, the largest difference in the model reaction cycles between DFT and ccCA methods is for processes involving radicals and bond dissociation.

Physical Description:

8 p.

Language(s):
Subject(s):
Keyword(s): density functional theory | correlation consistent Composite Approach | copper-mediated nitrene
Source: Journal of Chemical Theory and Computation, 2009, Washington DC: American Chemical Society, pp. 2959-2966
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/ct900277m |
  • ARK: ark:/67531/metadc107767
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Journal of Chemical Theory and Computation
Volume: 5
Issue: 11
Page Start: 2959
Page End: 2966
Peer Reviewed: Yes