Design and application of a multicoefficient correlatiomethod for dispersion interactions

The Journal of Chemical Physics vol. 120  p. 590  DOI: 10.1063/1.1630955
PMID/PMCID: 15267893 Published: 2004-01-08 

Timothy J. Giese [ ] , Darrin M. York [ ]

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A new multicoefficient correlation method (MCCM) is presented for the determination of accurate van der Waals interactions. The method utilizes a novel parametrization strategy that simultaneously fits to very high-level binding, Hartree–Fock and correlation energies of homo- and heteronuclear rare gas dimers of He, Ne, and Ar. The decomposition of the energy into Hartree–Fock and correlation components leads to a more transferable model. The method is applied to the krypton dimer system, rare gas–water interactions, and three-body interactions of rare gas trimers He3, Ne3, and Ar3. For the latter, a very high-level method that corrects the rare-gas two-body interactions to the total binding energy is introduced. A comparison with high-level CCSD(T) calculations using large basis sets demonstrates the MCCM method is transferable to a variety of systems not considered in the parametrization. The method allows dispersion interactions of larger systems to be studied reliably at a fraction of the computational cost, and offers a new tool for applications to rare-gas clusters, and the development of dispersion parameters for molecular simulation force fields and new semiempirical quantum models.