Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

3-2009

Journal or Book Title

Journal of Physical Chemistry A

Volume

113

Issue

26

First Page

7474

Last Page

7481

DOI

10.1021/jp900372d

Abstract

For the reaction M+(C2H4)n−1 + C2H4 → M+(C2H4)n, where M = Ag, Au, the binding energies are predicted at the second order perturbation (MP2) and coupled cluster (CCSD(T)) levels of theory. As the basis set is systematically improved, the predicted M = Ag binding energies steadily improve, as compared to the experimental values. In fact, the complete basis set limit (CBS) predicted CCSD(T) binding energy for Ag(C2H4)+ is within experimental error. For MP2, as the basis set is improved, the agreement with experiment worsens. Gold ions are predicted to bind more strongly than silver ions to ethene ligands. Mulliken population analyses of the silver and gold systems exhibit delocalization of the positive charges of the metal ions onto the ethene ligands. Reduced variational space analysis indicates that electrostatic interactions are the principal contributor to the bonding in these systems. Multiconfigurational self-consistent field calculations do not support the Dewar−Chatt−Duncanson model of transition metal−alkene bonding in Au(C2H4)+.

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 113 (2009): 7474, doi:10.1021/jp900372d. Copyright 2009 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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