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Vyboishchikov, Sergei F.
Salvador Sedano, Pedro Duran i Portas, Miquel 

The present work provides a generalization of Mayer’s energy decomposition for the densityfunctional theory (DFT) case. It is shown that one and twoatom HartreeFock energy components in Mayer’s approach can be represented as an action of a oneatom potential VA on a oneatom density ρ A or ρ B. To treat the exchangecorrelation term in the DFT energy expression in a similar way, the exchangecorrelation energy density per electron is expanded into a linear combination of basis functions. Calculations carried out for a number of density functionals demonstrate that the DFT and HartreeFock twoatom energies agree to a reasonable extent with each other. The twoatom 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. For nonspecific nonbonding interactions, the twoatom energies are low. They can be either repulsive or slightly attractive, but the DFT results more frequently yield small attractive values compared to the HartreeFock case. The hydrogen bond in the water dimer is calculated to be between the strong covalent and nonbonding interactions on the energy scale  
http://hdl.handle.net/2072/116929  
eng  
American Institute of Physics  
Tots els drets reservats  
Compostos organometàl·lics
Descomposició, Mètode de Enllaços d’hidrogen Enllaços químics Funcional de densitat, Teoria del Chemical bonds Density functionals Decomposition method Hydrogen bonding Organometallic compounds 

Density functional energy decomposition into one and twoatom contributions  
info:eurepo/semantics/article  
Recercat 