Intermolecular interaction energies from the total energy bi-functional. A case study of carbazole complexes

Wesolowski, Tomasz Adam; Morgantini, Pierre-Yves; Weber, Jacques

doi:10.1063/1.1462613

Scientific article

English

Intermolecular interaction energies from the total energy bi-functional. A case study of carbazole complexes

Contributors

Wesolowski, Tomasz Adam; Morgantini, Pierre-Yves; Weber, Jacques

Published in

The Journal of chemical physics, vol. 116, no. 15, p. 6411-6421

Publication date

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 (1 and 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, CH4, CO, and N2. 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 Exc[1 + 2] and nonadditive kinetic energy T[1,2] = Ts[1 + 2]–Ts[1]–Ts[2]) is made. The nonvariational version of the applied formalism is also discussed.

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

UNIGE research groups

Citation (ISO format)

WESOLOWSKI, Tomasz Adam, MORGANTINI, Pierre-Yves, WEBER, Jacques. Intermolecular interaction energies from the total energy bi-functional. A case study of carbazole complexes. In: The Journal of chemical physics, 2002, vol. 116, n° 15, p. 6411–6421. doi: 10.1063/1.1462613

Identifiers

PID : unige:3235
DOI : 10.1063/1.1462613

Journal ISSN

0021-9606

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29/10/2024 12:13:07

Intermolecular interaction energies from the total energy bi-functional. A case study of carbazole complexes

Contributors

Published in

Publication date

Abstract

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

Identifiers

Journal ISSN

Technical informations

Creation

First validation

Update

Status update

Last indexation