Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 9, Issue 5, Pages 2221-2225Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ct4000923
Keywords
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Funding
- Foundation of Scientific Research - Flanders (FWO)
- Natural Sciences and Engineering Research Council of Canada
- Canada Research Chairs
- European Research Council [240483]
- Fund for Scientific Research-Flanders (FWO)
- Research Board of Ghent University (BOF)
- BELSPO [IAP/7/05]
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For the development of ab initio derived force fields, atomic charges must be computed from electronic structure computations, such that (i) they accurately describe the molecular electrostatic potential (ESP) and (ii) they are transferable to the force-field application of interest. The Iterative Hirshfeld (Hirshfeld-I or HI) scheme meets both requirements for organic molecules For inorganic oxide clusters, however, Hirshfeld-I becomes ambiguous because electron densities of nonexistent isolated anions are needed as input. Herein, we propose a simple Extended Hirshfeld (Hirshfeld-E or HE) scheme to overcome this limitation. The performance of the new HE scheme is compared to four popular atoms-in-molecules schemes using two tests involving a set of 248 silica clusters. These tests show that the new HE scheme provides an improved trade-off between the ESP accuracy and the transferability of the charges. The new scheme is a generalization of the Hirshfeld-I scheme, and it is expected that its improvements are to a large extent applicable to molecular systems containing elements from the entire periodic table.
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