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Third‐order many‐body perturbation theory for intermolecular interactions. I. Hartree–Fock level
Author(s) -
Surján Péter R.,
Pérez Del Valle C.,
Lain Luis
Publication year - 1997
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1997)64:1<43::aid-qua5>3.0.co;2-1
Subject(s) - hartree–fock method , biorthogonal system , møller–plesset perturbation theory , wave function , quantum mechanics , water dimer , chemistry , intermolecular force , second quantization , perturbation theory (quantum mechanics) , physics , mathematical physics , quantum , molecule , hydrogen bond , wavelet transform , artificial intelligence , computer science , wavelet , creation and annihilation operators
A zero‐order wave function of a dimer is defined as theantisymmetrized product of monomer Hartree–Fock wave functions. Asymmetry‐adapted many‐body perturbation theory is developed up to the thirdorder to obtain interaction energies at the Hartree–Fock level.Correlation effects are accounted for at the second order. The theory isbased on second quantization to ensure full symmetry forcing.Intermolecular overlap effects are handled by the biorthogonal formulation.Test calculations on dimers of He, H 2 , HF, and water show thatthe third‐order results are very accurate. No “instability” dueto the use of biorthogonal orbitals was observed. © 1997 JohnWiley & Sons, Inc. Int J Quant Chem 64 : 43–51, 1997