Exact exchange and Wilson-Levy correlation: a pragmatic device for studying complex weakly-bonded systems.
The Wilson-Levy (WL) correlation functional is used together with Hartree-Fock (HF) theory to evaluate interaction energies at intermediate separations (i.e. around equilibrium separation) for several weakly-bonded systems. The HF+WL approach reproduces binding trends for all complexes studied: selected rare-gas dimers, isomers of the methane dimer, benzene dimer and naphthalene dimer, and base-pair stacking structures for pyrimidine, cytosine, uracil and guanine dimers. These HF+WL data are contrasted against results obtained from some popular functionals (including B3LYP and PBE), as well as two newly-developed functionals, X3LYP and xPBE. The utility of HF+WL, with reference to exact-exchange (EXX) density-functional theory, is discussed in terms of a suggested EXXWL exchange-correlation functional.
Department of Chemistry and Centre for Scientific Computing, University of Warwick, Coventry, UK.
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D020029:Base Pairing; D001554:Benzene / Q000737:chemistry*; D003596:Cytosine / Q000737:chemistry; D019281:Dimerization; D006147:Guanine / Q000737:chemistry; D008697:Methane / Q000737:chemistry*; D008958:Models, Molecular; D008962:Models, Theoretical; D009281:Naphthalenes / Q000737:chemistry*; D005741:Noble Gases / Q000737:chemistry; D011687:Purines / Q000737:chemistry*; D011743:Pyrimidines / Q000737:chemistry*; D014498:Uracil / Q000737:chemistry
D009281:Naphthalenes; D005741:Noble Gases; D011687:Purines; D011743:Pyrimidines; C031721:naphthalene; D014498:Uracil; D006147:Guanine; D003596:Cytosine; D001554:Benzene; D008697:Methane