New insights in quantum chemical topology studies using numerical grid-based analyses

Abstract

New insights in Quantum Chemical Topology of one-electron density functions have been proposed here by using a recent grid-based algorithm (Tang et al., J Phys Condens Matter 2009, 21, 084204), initially designed for the decomposition of the electron density. Beyond the charge analysis, we show that this algorithm is suitable for different scalar functions showing a more complex topology, that is, the Laplacian of the electron density, the electron localization function (ELF), and the molecular electrostatic potential (MEP). This algorithm makes use of a robust methodology enabling to numerically assign the data points of three-dimensional grids to basin volumes, and it has the advantage of requiring only the values of the scalar function without details on the wave function used to build the grid. Our implementation is briefly outlined (program named TopChem), its capabilities are examined, and technical aspects in terms of CPU requirement and accuracy of the results are discussed. Illustrative examples for individual molecules and crystalline solids obtained with gaussian and plane-wave-based density functional theory calculations are presented. Special attention was given to the MEP because its topological analysis is complex and scarce. Copyright © 2011 Wiley Periodicals, Inc.