The Transferability of Topologically Partitioned Electron Correlation Energies in Water Clusters

Arnaldo F Silva, Mark Vincent, James Mcdonagh, Paul Popelier

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    Abstract

    The electronic effects that govern the cohesion of water clusters are complex, demanding the inclusion of N-body, Coulomb, exchange and correlation effects. Here we present a much needed quantitative study of the effect of correlation (and hence dispersion) energy on the stabilization of water clusters. For this purpose we used a topological energy partitioning method called Interacting Quantum Atoms (IQA) to partition water clusters into topological atoms, based on a MP2/6-31G(d,p) wave function, and modified versions of GAUSSIAN09 and the Quantum Chemical Topology (QCT) program MORFI. Most of the cohesion in the water clusters provided by electron correlation comes from intramolecular energy stabilisation. Hydrogen bond-related interactions tend to largely cancel each other. Electron correlation energies are transferable in almost all instances within 1 kcal mol-1. This observed transferability is very important to the further development of the QCT force field FFLUX, especially to the future modelling of liquid water.
    Original languageEnglish
    JournalChemPhysChem
    Early online date2 Nov 2017
    DOIs
    Publication statusPublished - 2017

    Keywords

    • Water cluster
    • Electron correlation
    • FFLUX
    • Force Field
    • Interacting Quantum Atoms (IQA)
    • Quantum chemical topology (QCT)

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