Lecture Sergei F. Vyboishchikov
|20 maart 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|
|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  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 . 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 . Another useful extension of the method is partitioning of molecular atomization energy .
 Mayer I., Chem. Phys. Letters 2003, 382, 265.
 Vyboishchikov S.F., Salvador P., Duran M., J. Chem. Phys., 2005, 122, 244110.
 Vyboishchikov S.F., Salvador P., Chem. Phys. Letters 2006 , 430, 204.
 Vyboishchikov S.F., Int. J. Quant. Chem. 2008, 108, 708.
|Laatst gewijzigd:||22 oktober 2012 14:30|