The Transferability of Topologically Partitioned Electron Correlation Energies in Water Clusters

Author(s)

Silva, Arnaldo F. ^{[1, 2]} ; Vincent, Mark A. ^{[1, 2]} ; McDonagh, James L. ^{[1, 2]} ; Popelier, Paul L. A. ^{[1, 2]}

Affiliation

^[1] Univ Manchester, Manchester Inst Biotechnol, 131 Princess St, Manchester M1 7DN, Lancs - England

^[2] Univ Manchester, Sch Chem, Oxford Rd, Manchester M13 9PL, Lancs - England

• Document type: Journal article
• Source: ChemPhysChem; v. 18, n. 23, p. 3360-3368, DEC 6 2017.
• Web of Science Citations: 8

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 stabilization. Hydrogen bond-related interactions tend to largely cancel each other. Electron correlation energies are transferable in almost all instances within 1kcalmol(-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. (AU)

• FAPESP's process: 14/21241-9 - The inclusion of polarization effects in the description of amino acids and peptides through the use of atomic multipoles obtained from electron densities
• Grantee: Arnaldo Fernandes da Silva Filho
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 15/22247-3 - Using the Quantum Chemical Topology theory for modeling force fields for peptides using electron densities
• Grantee: Arnaldo Fernandes da Silva Filho
• Support Opportunities: Scholarships abroad - Research Internship - Post-doctor