Localized orbitals for intermolecular interactions
type: Dataset
description: We study in this thesis intermolecular interactions through a localized orbitals point of view. This concerns on one hand the intermolecular interactions generated by the occupied localized orbitals such as the electrostatic interaction, and on the other hand the intermolecular interactions like the dispersion interaction that involve virtual orbitals. We evaluate in a first part the electrostatic interactions on frozen monomer charge densities provided by multipolar distributions on occupied localized orbitals. These give chemically meaningful representations of molecular charge densities. We show that multipolar distributions on localized orbitals are suitable to describe intermolecular electrostatic interactions if the interaction is truncated to a suitable order, making localized orbitals potentially interesting to model electrostatic interactions in a force field. We use then the properties of a priori constructed localized orbitals on a complex in order to define a reference multipolar interaction for the electrostatic interaction of relaxed charge densities. We evaluate hence the capacity of multipolar distributions based on relaxed localized orbitals to decribe the relaxed electrostatic interaction. In a second part, localizing both occupied and virtual orbitals in an intermolecular framework allows us to attribute the orbitals of a noncovalent system to each of its fragments (and to divide the excitations by classes), and select in a further step only the most relevant excitations to the intermolecular post-Hartree-Fock correlation energy. We propose two different methods we developped in this work to select the excitations in the general framework of the range separated density functional theory (DFT) coupled to the random phase approximation (RPA). The first method is based on a simple energetic criterion while the other is based on a selection of only one class, namely the dispersion-type excitations. We show afterwards both the usefulness and the limits…
landing page: https://theses.hal.science/tel-00796910
keyword: champ-de-force
keyword: chimtheochemical-sciencestheoretical-andor-physical-chemistry
keyword: correlation-electronique
keyword: density-functional-theory
keyword: dft
keyword: electronic-correlation
keyword: force-fields
keyword: infoeu-reposemanticsdoctoralthesis
keyword: interactions-de-van-der-waals
keyword: interactions-intermoleculaires
keyword: interactions-non-covalentes
keyword: intermolecular-interactions
keyword: localized-orbitals
keyword: multipoles
keyword: non-covalent-interactions
keyword: orbitales-localisees
keyword: rpa
keyword: theorie-de-la-fonctionnelle-de-la-densite
keyword: theses
keyword: van-der-waals-interactions
issued: 2026-05-13T15:07:50.398232
modified: 2026-05-13T15:07:50.398237
language: fr
contact point: Organization
  fn: CCSD

test_moissonnage_selune
type: Agent

Localized orbitals for intermolecular interactions
type: Distribution
format: HTML
access URL: https://theses.hal.science/tel-00796910
issued: 2026-05-13T15:07:50.523440
modified: 2026-05-13T15:07:50.334518