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Classical Density Functional Theory for Molecular Systems

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Book cover Variational Methods in Molecular Modeling

Part of the book series: Molecular Modeling and Simulation ((MMAS))

Abstract

Classical density functional theory (DFT) is able to predict the structural and thermodynamic properties of complex molecular systems with accuracy comparable to that inherited from semi-empirical force fields but at a computational cost up to several orders of magnitude lower than molecular simulations. In combination with first-principles methods, in particular with the Kohn-Sham DFT calculations for electronic properties, classical DFT opens up exciting opportunities for the development and validation of customized molecular models for chemicals design and discovery including high-throughput screening of nanostructured materials, solvents and electrolytes. This chapter provides a tutorial introduction of the basic concepts of the classical DFT in the context of multiscale modeling that aims to predict the rich behavior of molecular systems under diverse thermodynamic environments. A special emphasis is placed on various quantitative structure-property relationships for inhomogeneous molecular systems based on semi-empirical molecular models or force fields, microscopic structure, and inter- as well as intra-molecular correlation functions. Several mathematical procedures are outlined for the derivation of density functionals that are able to accurately account for thermodynamic non-ideality with atomistic details.

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Notes

  1. 1.

    The electron mass is 1/1836 of that for proton, the lightest nuclear particle. As a result, most of the atomic mass is concentrated in the nucleus.

  2. 2.

    Class II and III force fields contain cubic and/or quartic terms in the potential energy for bond lengths and angles.

  3. 3.

    While quantum mechanics is used in a conventional statistical-mechanical model of polyatomic ideal gases to describe atomic motions, bond stretching and vibrations, a semi-empirical force field assumes that atoms are classical particles moving with the constraints of intramolecular potentials. As a result, a semi-empirical force field is not able to describe the ideal-gas heat capacity.

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  1. Department of Chemical and Environmental Engineering and Department of Mathematics, University of California, Riverside, California, 92521, USA

    Jianzhong Wu

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    Jianzhong Wu

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Wu, J. (2017). Classical Density Functional Theory for Molecular Systems. In: Wu, J. (eds) Variational Methods in Molecular Modeling. Molecular Modeling and Simulation. Springer, Singapore. https://doi.org/10.1007/978-981-10-2502-0_3

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  • DOI: https://doi.org/10.1007/978-981-10-2502-0_3

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