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Advances in the Theory of Atomic and Molecular Systems pp 397–415Cite as

The Dissociation Catastrophe in Fluctuating-Charge Models and its Implications for the Concept of Atomic Electronegativity

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Part of the book series: Progress in Theoretical Chemistry and Physics ((PTCP,volume 19))

Abstract

We have recently developed the QTPIE (charge transfer with polarization current equilibration) fluctuating-charge model, a new model with correct dissociation behavior for nonequilibrium geometries. The correct asymptotics originally came at the price of representing the solution in terms of charge-transfer variables instead of atomic charges. However, we have found an exact reformulation of fluctuating-charge models in terms of atomic charges again, which is made possible by the symmetries of classical electrostatics. We show how this leads to the distinction between two types of atomic electronegativities in our model. While one is a intrinsic property of individual atoms, the other takes into account the local electrical surroundings. This distinction could resolve some confusion surrounding the concept of electronegativity as to whether it is an intrinsic property of elements, or otherwise. We also use the QTPIE model to create a three-site water model and discuss simple applications.

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Author information

Authors and Affiliations

  1. Department of Chemistry, Center for Advanced Theory and Molecular Simulation, Frederick SeitzMaterials Research Laboratory, The Beckman Institute, University of Illinois, 61801, Urbana, Illinois, USA

    Jiahao Chen

  2. Department of Chemistry, Stanford University, S.G. Mudd Bldg., Room 121, 94305-5080, Stanford, CA, USA

    Todd J. Martínez

Authors
  1. Jiahao Chen
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  2. Todd J. Martínez
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Corresponding author

Correspondence to Jiahao Chen .

Editor information

Editors and Affiliations

  1. Department of Chemistry, Michigan State University, 48824, East Lansing, MI, USA

    Piotr Piecuch

  2. Laboratoire de Chimie Physique CNRS and UPMC, 11 Rue Pierre et Marie Curie, F-75005, Paris, France

    Jean Maruani

  3. Instituto de Física Fundamental, CSIC, Serrano 123, E-28006, Madrid, Spain

    Gerardo Delgado-Barrio

  4. Physical & Theoretical Chemistry Laboratry, University of Oxford, South Parks Road, OX1 3QZ, Oxford, UK

    Stephen Wilson

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Chen, J., Martínez, T.J. (2009). The Dissociation Catastrophe in Fluctuating-Charge Models and its Implications for the Concept of Atomic Electronegativity. In: Piecuch, P., Maruani, J., Delgado-Barrio, G., Wilson, S. (eds) Advances in the Theory of Atomic and Molecular Systems. Progress in Theoretical Chemistry and Physics, vol 19. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-2596-8_19

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