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Hirshfeld-E partitioning: AIM charges with an improved trade-off between robustness and accurate electrostatics

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Abstract
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.
Keywords
MOLECULAR-DYNAMICS SIMULATIONS, PERIODIC MATERIALS, DENSITY-FUNCTIONAL THEORY, ATOMIC CHARGES, NONPERIODIC MATERIALS, ORBITAL METHODS, FORCE-FIELDS, BASIS-SET, MODELS, BULK

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Chicago
Verstraelen, Toon, Paul W Ayers, Veronique Van Speybroeck, and Michel Waroquier. 2013. “Hirshfeld-E Partitioning: AIM Charges with an Improved Trade-off Between Robustness and Accurate Electrostatics.” Journal of Chemical Theory and Computation 9 (5): 2221–2225.
APA
Verstraelen, T., Ayers, P. W., Van Speybroeck, V., & Waroquier, M. (2013). Hirshfeld-E partitioning: AIM charges with an improved trade-off between robustness and accurate electrostatics. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 9(5), 2221–2225.
Vancouver
1.
Verstraelen T, Ayers PW, Van Speybroeck V, Waroquier M. Hirshfeld-E partitioning: AIM charges with an improved trade-off between robustness and accurate electrostatics. JOURNAL OF CHEMICAL THEORY AND COMPUTATION. 2013;9(5):2221–5.
MLA
Verstraelen, Toon, Paul W Ayers, Veronique Van Speybroeck, et al. “Hirshfeld-E Partitioning: AIM Charges with an Improved Trade-off Between Robustness and Accurate Electrostatics.” JOURNAL OF CHEMICAL THEORY AND COMPUTATION 9.5 (2013): 2221–2225. Print.
@article{4099790,
  abstract     = {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.},
  author       = {Verstraelen, Toon and Ayers, Paul W and Van Speybroeck, Veronique and Waroquier, Michel},
  issn         = {1549-9618},
  journal      = {JOURNAL OF CHEMICAL THEORY AND COMPUTATION},
  language     = {eng},
  number       = {5},
  pages        = {2221--2225},
  title        = {Hirshfeld-E partitioning: AIM charges with an improved trade-off between robustness and accurate electrostatics},
  url          = {http://dx.doi.org/10.1021/ct4000923},
  volume       = {9},
  year         = {2013},
}

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