Dependence of the closed-shell repulsive interaction on the overlap of the electron densities

Kim, Yung Sik; Kim, Seong Keun; Lee, Won Don

doi:10.1016/0009-2614(81)85080-4

Cited by 46 publications

(35 citation statements)

References 7 publications

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“…This model is supported with some experimental evidence, 45,61 but it has serious flaws as an interpretable model However, these models are, by and large, unitless which means that they do not suffer from the second and more important reason that the density overlap model is problematic-the density overlap model has the wrong distance dependence. Since the density overlap is proportional to charge squared over distance cubed, applying the electric constant no longer gives units of energy but energy over distance squared.…”

Section: B a Note On "Density Overlap" Modelsmentioning

confidence: 59%

“…44 In 1981, Kim, Kim, and Lee arrived at the same conclusion upon examination of experimental noble gas repulsion data. 45 This observation was first turned into a molecular mechanics model by Wheatley and Price, whose use of anisotropic atomic densities yielded an anisotropic repulsion model. 46 This model influenced Stone's original work on the water model mentioned above.…”

Section: A a Brief History Of Pauli Repulsion Modelsmentioning

confidence: 99%

“…Although this is less straightforward to compute for polyatomic molecules, we defined R as the O-O distance and computed S 2 according to Eq. (45) with each monomer's MOs. This measure is also in very good agreement with the SAPT results, with the divergence at short range likely due to our neglect of the hydrogens in the definition of R. Also shown in Fig.…”

Section: Water Dimersmentioning

confidence: 99%

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Classical Pauli repulsion: An anisotropic, atomic multipole model

Rackers

Ponder

2019

The Journal of Chemical Physics

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Pauli repulsion is a key component of any theory of intermolecular interactions. Although Pauli or exchange repulsion has its origin in the quantum mechanical nature of electrons, it is possible to describe the resulting energetic effects via a classical model in terms of the overlap of electron densities. In fact, closed shell intermolecular repulsion can be explained as a diminution of election density in the internuclear region resulting in decreased screening of nuclear charges and increased nuclear-nuclear repulsion. We provide a concise anisotropic repulsion formulation using the atomic multipoles from the Atomic Multipole Optimized Energetics for Biomolecular Applications force field to describe the electron density at each atom in a larger system. Mathematically, the proposed model consists of damped pairwise exponential multipolar repulsion interactions truncated at short range, which are suitable for use in compute-intensive biomolecular force fields and molecular dynamics simulations. Parameters for 26 atom classes encompassing most organic molecules are derived from a fit to Symmetry Adapted Perturbation Theory exchange repulsion energies for the S101 dimer database. Several applications of the multipolar Pauli repulsion model are discussed, including noble gas interactions, analysis of stationary points on the water dimer potential surface, and the directionality of several halogen bonding interactions.

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Section: B a Note On "Density Overlap" Modelsmentioning

confidence: 59%

Section: A a Brief History Of Pauli Repulsion Modelsmentioning

confidence: 99%

Section: Water Dimersmentioning

confidence: 99%

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Classical Pauli repulsion: An anisotropic, atomic multipole model

Rackers

Ponder

2019

The Journal of Chemical Physics

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“…Radzio-Andzelm (1981) has discussed ways for improving the Gordon-Kim approach throug:1 modifications of the kinetic and exchange terms. Kim et al (1981) haye investigated the relationship between the closed-shell repulsive interaction energy and the magnitude of the overlapping of electron densities of interacting species. (5.3-82) multiplied by an exponential damping factor which is included in order to eliminate its long-distance divergence (see Herman et al, 1969Herman et al, , 1970.…”

Section: { L R Ud(5) (Re)/efo['mentioning

confidence: 99%

Energy Density Functional Theory of Many-Electron Systems

1990

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“…The exchange is modeled as a proportionality with the overlap between electron densities, based on previous observations of this proportionality. [24][25][26][27] After the inducible dipole model is introduced in Section 2, and Slater widths for each chemical element are determined in Section 3.1, we validate our model by its performance in the prediction of molecular polarizabilities in Section 3.2 and a large number of three-body interaction energies in Section 3.3. In this way, we can directly compare the non-additive component of our model to abinitio three-body energies, ensuring our model exhibits the correct many-body behavior.…”

Section: Introductionmentioning

confidence: 94%

Accurate transferable polarization model derived from the monomer electron density

Goeminne,

Verstraelen

2020

Preprint

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Force field have for decades proven to be an indispensable tool for molecular simulations which are out of reach for ab-initio methods. Recent efforts to improve the accuracy of these simulations have focused on the inclusion of many-body interactions in force fields. In this regard, we propose a transferable inducible dipole model which requires only the monomer electron density as input, without the need for atom type specific parameters. Slater dipoles are introduced, the widths of which are derived from the ab-initio monomer density. An additional exchange-repulsion interaction is introduced in our model, originating from the overlap of the delocalized dipoles with other dipoles and the ground state electron density. This interaction has previously been neglected in point dipole models, as the lack of spatial extent of the dipoles prevents the inclusion of an overlap term. The inclusion of this interaction is shown to significantly improve the prediction of three-body energies. Our model is incorporated in a previously proposed non-covalent force field and is benchmarked on interaction energies of dimers contained in the hsg and hbc6 datasets. Furthermore, we demonstrate the transferability of our model to the condensed phase of water, and to the interaction of CO 2 and H 2 O molecules with the ZIF-8 metal-organic framework. The inherent transferability of our model makes it widely applicable to systems like the aforementioned metal-organic frameworks, where no specifically fitted parameters for polarization models are available in the literature.

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Dependence of the closed-shell repulsive interaction on the overlap of the electron densities

Cited by 46 publications

References 7 publications

Classical Pauli repulsion: An anisotropic, atomic multipole model

Classical Pauli repulsion: An anisotropic, atomic multipole model

Energy Density Functional Theory of Many-Electron Systems

Accurate transferable polarization model derived from the monomer electron density

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