Design and application of a multicoefficient correlation method for dispersion interactions.
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.
Giese
Timothy J
TJ
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55415, USA.
York
Darrin M
DM
D000465:Algorithms; D001128:Argon / Q000737:chemistry*; D003198:Computer Simulation; D019281:Dimerization; D006371:Helium / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D009356:Neon / Q000737:chemistry*; D044367:Phase Transition; D011789:Quantum Theory; D013223:Statistics as Topic
D006371:Helium; D009356:Neon; D001128:Argon