Bultinck, Patrick

Van Driessche, Isabel

Vanpoucke, Danny

English

Ghent University Academic Bibliography

Chemistry in Solids; Extending theHirshfeld-I method.Danny E. P. Vanpoucke, Patrick Bultinck, Isabel Van DriesscheDepartment of Inorganic and Physical Chemistry, Ghent University, Krijgslaan281{S3,9000 Ghent, Belgium. Danny.Vanpoucke@Ugent.beABSTRACT The concept of \atoms in molecules" (AIM), is probably one of the mostsuccessful concepts in chemistry. It states that the properties of a molecule can be seenas simple sums of the properties of the molecules' constituent atoms. This shows thatthe concept of AIM is strongly linked to the concept of transferability. Since both arecentral in chemistry, and chemists mainly focus on molecules, they are generally used toinvestigate molecules. There is, however, no reason why these concepts should not holdfor solids. Even more, if these concepts are truly valid, they should work equally well forsolids as for molecules and thus provide additional insight in the chemical properties ofdefects such as dopants and interfaces.The AIM concept is centered around the question of how one should divide a molecule,or more general a system, into \atoms". Practically, this means dividing the electrons. Inreal-space one divides the charge density distribution, either using non-overlapping regions(e.g. Bader's approach) or overlapping regions (e.g. Hirshfeld and derived methods).[1, 2,3]We have implemented an extension of the iterative Hirshfeld-I approach to periodicsystems.[4] This implementation makes use of precalculated pseudo-potential based chargedensity distribution grids. We show how the accuracy is inuenced by the used grid spac-ings, and that the use of pseudo-potentials has no negative inuence on the results.We identify a delocalization problem due to the use of plane waves and periodic boundaryconditions, and present a simple and satisfactory solution.This extension of the Hirshfeld-I method allows for the easy calculation of atomiccharges and charge transfer in periodic systems, such as wires, surfaces and bulk materials.References:[1] Bader, R. F. Chem. Rev., 91 (1991) 893{928[2] Hirshfeld, F. L. Theoret. Chim. Acta 44 (1977) 129-138[3] Bultinck, P., Alsenoy, C. V., Ayers, P. W., and Carbo-Dorca, R. J. Chem. Phys. 126(2007) 144111[4] Vanpoucke, D. E. P., Bultinck, P., and Van Driessche, I.Extending Hirshfeld-I to bulk and periodic materialssubmitted to J. Chem. Theory Comp. (2011)1

Chemistry in solids: extending the Hirshfeld-I method

https://biblio.ugent.be/publication/2040841/file/2040875

Chemistry in solids: extending the Hirshfeld-I method

Abstract

Similar works

Full text

Available Versions

Ghent University Academic Bibliography