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New intermolecular benchmark calculations on the water dimer: SAPT and supermolecular post‐Hartree–Fock approaches
Author(s) -
Reinhardt P.,
Piquemal J.P.
Publication year - 2009
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.22299
Subject(s) - water dimer , chemistry , electronic correlation , ab initio , intermolecular force , hartree–fock method , perturbation theory (quantum mechanics) , degenerate energy levels , van der waals force , statistical physics , interaction energy , molecular physics , computational chemistry , physics , quantum mechanics , electron , molecule , hydrogen bond
In this contribution, we propose accurate intermolecular benchmarks for the 10 standardized water dimers initially proposed by van Duijneveldt et al., following a study by Smith et al. (J Chem Phys, 1990, 92, 1240). Using the popular triple‐zeta aug‐cc‐pVTZ basis set, symmetry‐adapted perturbation theory (SAPT) computations have been performed and compared with supermolecular post‐Hartree–Fock techniques up to most recent explicitly correlated methods. Effects of approximated inclusion of third‐order corrections to induction and exchange‐induction energies are discussed. As SAPT results are close to the best available ab initio ones, detailed analysis of the available individual SAPT contributions to the interaction energy confirms that electron correlation acts not only on its long‐range dispersion part but also on its separated physical components. This permits to assess the validity of the usual HF+Dispersion model as approximation to add pure correlation effects to orbital‐based interaction schemes. The study proposes extensive benchmark data in a Supporting Information part to provide useful data for the development and the test of new force field energy functions for water. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009