Premium
Extrapolation methods and scaled perturbation theory for determining intermolecular potential energy surfaces
Author(s) -
Hodges Matthew P.,
Bichoutskaia Elena,
Tulegenov Akyl S.,
Wheatley Richard J.
Publication year - 2003
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/qua.10747
Subject(s) - supermolecule , perturbation theory (quantum mechanics) , extrapolation , intramolecular force , scaling , chemistry , dimer , intermolecular force , water dimer , electronic correlation , computational chemistry , quantum mechanics , statistical physics , physics , electron , molecule , mathematics , mathematical analysis , hydrogen bond , geometry , organic chemistry
We construct potential energy curves for six rare‐gas dimers and several 1‐D cuts through two H 2 … rare‐gas potential energy surfaces using two methods. The first is based on supermolecule dimer calculations at a low level of theory, extrapolated using monomer calculations at higher levels of theory. The second is based on perturbation theory calculations, where the effects of intramolecular electron correlation on different interaction terms are treated using approximate scaling relationships. Both methods are competitive with supermolecule dimer calculations at higher levels of theory and provide computationally efficient means of studying weakly bound systems. The methods are therefore suitable for calculations on larger systems for which accurate supermolecule methods would be computationally expensive. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004