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Intermolecular interaction energies from the total energy bifunctional: A case study of carbazole complexes.

Intermolecular interaction energies from the total energy bifunctional: A case study of carbazole complexes.

Authors :
Wesolowski, T. A.
Morgantini, P.-Y.
Weber, J.
Source :
Journal of Chemical Physics. 4/15/2002, Vol. 116 Issue 15, p6411. 11p. 1 Diagram, 9 Charts, 2 Graphs.
Publication Year :
2002

Abstract

An approach in which the total energy of interacting subsystems is expressed as a bifunctional depending explicitly on two functions: electron densities of the two molecules forming a complex (ρ[sub 1] and ρ[sub 2]) was used to determine the equilibrium geometry and the binding energy of several weak intermolecular complexes involving carbazole and such atoms or molecules as Ne, Ar, CH[sub 4], CO, and N[sub 2]. For these complexes, the experimental dissociation energies fall within the range from 0.48 to 2.06 kcal/mol. Since the effect of the intermolecular vibrations on the dissociation energy is rather small, the experimental measurements provide an excellent reference set. The obtained interaction energies are in a good agreement with experiment and are superior to the ones derived from conventional Kohn–Sham calculations. A detailed analysis of relative contribution of the terms which are expressed using approximate functionals (i.e., exchange-correlation E[sub xc][ρ[sub 1]+ρ[sub 2]] and nonadditive kinetic energy T[sub s][sup nad][ρ[sub 1],ρ[sub 2]]=T[sub s][ρ[sub 1]+ρ[sub 2]]-T[sub s][ρ[sub 1]]-T[sub s][ρ[sub 2]]) is made. The nonvariational version of the applied formalism is also discussed. © 2002 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Subjects

Subjects :
*INTERMOLECULAR forces
*CARBAZOLE

Details

Language :
English
ISSN :
00219606
Volume :
116
Issue :
15
Database :
Academic Search Index
Journal :
Journal of Chemical Physics
Publication Type :
Academic Journal
Accession number :
6427040
Full Text :
https://doi.org/10.1063/1.1462613