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Atoms-in-molecules analysis for planewave DFT calculations—A numerical approach on a successively interpolated charge density grid

✍ Scribed by Wai-Leung Yim; Thorsten Klüner


Publisher
John Wiley and Sons
Year
2008
Tongue
English
Weight
182 KB
Volume
29
Category
Article
ISSN
0192-8651

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✦ Synopsis


Abstract

We used a successive charge interpolation scheme and Ridders method for differentiation, to acquire accurate charge densities and their higher derivatives in electronic structure calculations. This enables us to search bond critical points using arbitrary charge density grids. We applied the planewave‐DFT code, VASP, to generate the charge density of selected benchmark molecules. The properties of bond critical points are in good agreement with those obtained by complementary implementations. We validated our GRID implementation by performing electronic structure calculations using the Gaussian 03 program package and various tools for analysis of the charge density provided by the AIMPAC package. In particular, we carefully investigate the influence of effective core potentials on the location of bond critical points, especially for a short chemical bond, which is crucial in the present pseudopotential‐based planewave DFT calculations. We expect our generic implementation will not only be useful for the analysis of chemical bonding in molecules, but will particularly provide a microscopic understanding of extended systems including periodic boundary conditions. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2008