Smeared Coulomb potential orbitals: I- Asymptotic expansion - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Mathematical Chemistry Année : 2021

Smeared Coulomb potential orbitals: I- Asymptotic expansion

Résumé

We consider an 1-electron model Hamiltonian, whose potential energy corresponds to the Coulomb potential of an infinite wire with charge Z distributed according to a Gaussian function. The time independent Schrödinger equation for this Hamiltonian is solved perturbationally in the asymptotic limit of small amplitude vibration (Gaussian function width close to zero). We propose to use the naturally polarized functions so-obtained, as orbital basis sets for quantum chemical calculations. In particular, they should be well suited to perform electron-nucleus mean field configuration interaction calculations. Since the free-parameters of the model have the remarkable property to factorize the perturbative corrections to the eigenfunctions, these corrective part in factor can be simply added as additional functions to standard basis sets, leaving it to the molecular orbital calculation to optimize the free parameters within molecular orbital coefficients.
Fichier principal
Vignette du fichier
gen-STO-v3.pdf (14.89 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-01539172 , version 1 (14-06-2017)
hal-01539172 , version 2 (09-08-2018)
hal-01539172 , version 3 (07-03-2019)
hal-01539172 , version 4 (13-09-2019)
hal-01539172 , version 5 (01-12-2020)

Identifiants

Citer

Patrick Cassam-Chenaï, Gilles Lebeau. Smeared Coulomb potential orbitals: I- Asymptotic expansion. Journal of Mathematical Chemistry, 2021, ⟨10.1007/s10910-021-01218-6⟩. ⟨hal-01539172v5⟩
339 Consultations
114 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More