Abstract
Calculations of large scale electronic structure within periodic boundary conditions, mostly based on solid state physics, allow the modeling of atomic forces and molecular dynamics for atomic assemblies of 100–1000 atoms, thus providing complementary information in material and macromolecular sciences. Nevertheless, these methods lack connections with the chemistry of simple molecules as isolated entities. In order to contribute to establish a conceptual connection between solid state physics and chemistry, the calculation of the extent of electron sharing between atoms, also known as delocalization index, is performed on simple molecules and on complexes with transition metal atoms, using density functional calculations where the Kohn–Sham molecular orbitals are represented in terms of plane waves and in periodic boundary conditions. These applications show that the useful measure of electron sharing between atomic pairs can be recovered from density functional calculations using the same set-up applied to large atomic assemblies in condensed phases, with no projections of molecular orbitals onto atomic orbitals.
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Acknowledgments
This work has been performed under the HPC-EUROPA2 project (project number: 127) with the support of the European Commission—Capacities Area—Research Infrastructures. MS acknowledges financial support from the Spanish MICINN project nr. CTQ2008-03077/BQU and the Catalan DIUE through project nr. 2009SGR637. Support for the research of MS was also received through the prize “ICREA Academia” 2009 for excellence in research funded by the DIUE of the Generalitat da Catalunya. GLP thanks P. Giannozzi (University of Udine, Italy) for the many suggestions.
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Soon after the paper was accepted, it appeared a work by Baranov and Kohout (Barnanov AI, Kohout M (2011) J Comput Chem DOI: 10.1002/jcc.21784) that discusses the calculation of electron localization and delocalization indices in solid state periodic systems using plane waves and the QTAIM partition.
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La Penna, G., Furlan, S. & Solà, M. Measuring electron sharing between atoms in first-principle simulations. Theor Chem Acc 130, 27–36 (2011). https://doi.org/10.1007/s00214-011-0955-3
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DOI: https://doi.org/10.1007/s00214-011-0955-3