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Lecture Sergei F. Vyboishchikov


20 March 2009 FWN-Building 5114.0004, Nijenborgh 4, 9747 AG, Groningen
Speaker: Dr. Sergei F. Vyboishchikov
Affiliation: Institut de Química Computacional, Universitat de Girona, Spain
Title: DFT energy partitioning as a tool for studying intramolecular interactions
Date: Fri Mar 20, 2009
Start: 14.00
Location: FWN-Building 5114.0004
Host: Michael Filatov
Telephone: +31 50 363 4377


The present work provides a partitioning of the DFT energy into one-atom and diatomic components. First, we demonstrate that Mayer’s Hartree–Fock energy partitioning [1] can be represented in terms of one-atom densities and one-atom effective potentials that are introduced in the spirit of Mulliken population analysis. To treat the exchange-correlation term in the DFT energy expression, the exchange-correlation energy density is expanded into a linear combination of basis functions [2]. A number of examples including small inorganic, organic, and organometallic molecules are discussed. The calculations demonstrate that the DFT and Hartree-Fock diatomic energies agree to a reasonable extent with each other. The diatomic energies for strong covalent bonds are within the range of typical bond dissociation energies and are therefore a convenient computational tool for assessment of individual bond strength in polyatomic molecules.

We also present a generalization of the Mayer partitioning for the case of a correlated ab initio wavefunction [3]. Another useful extension of the method is partitioning of molecular atomization energy [4].


[1] Mayer I., Chem. Phys. Letters 2003, 382, 265.

[2] Vyboishchikov S.F., Salvador P., Duran M., J. Chem. Phys., 2005, 122, 244110.

[3] Vyboishchikov S.F., Salvador P., Chem. Phys. Letters 2006 , 430, 204.

[4] Vyboishchikov S.F., Int. J. Quant. Chem. 2008, 108, 708.

Last modified:22 October 2012 2.30 p.m.