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The Monomer Electron Density Force Field (MEDFF) : a physically inspired model for noncovalent interactions

Steven Vandenbrande UGent, Michel Waroquier UGent, Veronique Van Speybroeck UGent and Toon Verstraelen UGent (2017) JOURNAL OF CHEMICAL THEORY AND COMPUTATION. 13(1). p.161-179
abstract
We propose a methodology to derive pairwise-additive noncovalent force fields from monomer electron densities without any empirical input. Energy expressions are based on the symmetry-adapted perturbation theory (SAPT) decomposition of interaction energies. This ensures a physically motivated force field featuring an electrostatic, exchange repulsion, dispersion, and induction contribution, which contains two types of parameters. First, each contribution depends on several fixed atomic parameters, resulting from a partitioning of the monomer electron density. Second, each of the last three contributions (exchange-repulsion, dispersion, and induction) contains exactly one linear fitting parameter. These three so-called interaction parameters in the model are initially estimated separately using SAPT reference calculations for the S66x8 database of noncovalent dimers. In a second step, the three interaction parameters are further refined simultaneously to reproduce CCSD(T)/CBS interaction energies for the same database. The limited number of parameters that are fitted to dimer interaction energies (only three) avoids ill-conditioned fits that plague conventional parameter optimizations. For the exchange repulsion and dispersion component, good results are obtained for all dimers in the S66x8 database using one single value for the associated interaction parameters. The values of those parameters can be considered universal and can also be used for dimers not present in the original database used for fitting. For the induction component such an approach is only viable for the dispersion dominated dimers in the S66x8 database. For other dimers (such as hydrogen-bonded complexes), we show that our methodology remains applicable. However, the interaction parameter needs to be determined on a case-specific basis. As an external validation:, the force field predicts interaction energies in good agreement with CCSD(T)/CBS values for dispersion dominated dimers extracted from an HIV-II protease crystal structure with a bound ligand (indinavir). Furthermore, experimental second virial coefficients of small alkanes and alkenes are well reproduced.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
ADAPTED PERTURBATION-THEORY, 2ND VIRIAL-COEFFICIENTS, ZEOLITIC IMIDAZOLATE FRAMEWORKS, ACCURATE INDUCTION ENERGIES, STATISTICAL ATOMIC MODELS, SMALL ORGANIC-MOLECULES, AB-INITIO, CHARGE-TRANSFER, INTERMOLECULAR INTERACTIONS, N-ALKANES
journal title
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
J. Chem. Theory Comput.
volume
13
issue
1
pages
161 - 179
Web of Science type
Article
Web of Science id
000391898200016
ISSN
1549-9618
1549-9626
DOI
10.1021/acs.jctc.6b00969
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
8509565
handle
http://hdl.handle.net/1854/LU-8509565
date created
2017-02-15 10:36:18
date last changed
2018-02-02 23:30:14
@article{8509565,
  abstract     = {We propose a methodology to derive pairwise-additive noncovalent force fields from monomer electron densities without any empirical input. Energy expressions are based on the symmetry-adapted perturbation theory (SAPT) decomposition of interaction energies. This ensures a physically motivated force field featuring an electrostatic, exchange repulsion, dispersion, and induction contribution, which contains two types of parameters. First, each contribution depends on several fixed atomic parameters, resulting from a partitioning of the monomer electron density. Second, each of the last three contributions (exchange-repulsion, dispersion, and induction) contains exactly one linear fitting parameter. These three so-called interaction parameters in the model are initially estimated separately using SAPT reference calculations for the S66x8 database of noncovalent dimers. In a second step, the three interaction parameters are further refined simultaneously to reproduce CCSD(T)/CBS interaction energies for the same database. The limited number of parameters that are fitted to dimer interaction energies (only three) avoids ill-conditioned fits that plague conventional parameter optimizations. For the exchange repulsion and dispersion component, good results are obtained for all dimers in the S66x8 database using one single value for the associated interaction parameters. The values of those parameters can be considered universal and can also be used for dimers not present in the original database used for fitting. For the induction component such an approach is only viable for the dispersion dominated dimers in the S66x8 database. For other dimers (such as hydrogen-bonded complexes), we show that our methodology remains applicable. However, the interaction parameter needs to be determined on a case-specific basis. As an external validation:, the force field predicts interaction energies in good agreement with CCSD(T)/CBS values for dispersion dominated dimers extracted from an HIV-II protease crystal structure with a bound ligand (indinavir). Furthermore, experimental second virial coefficients of small alkanes and alkenes are well reproduced.},
  author       = {Vandenbrande, Steven and Waroquier, Michel and Van Speybroeck, Veronique and Verstraelen, Toon},
  issn         = {1549-9618},
  journal      = {JOURNAL OF CHEMICAL THEORY AND COMPUTATION},
  keyword      = {ADAPTED PERTURBATION-THEORY,2ND VIRIAL-COEFFICIENTS,ZEOLITIC IMIDAZOLATE FRAMEWORKS,ACCURATE INDUCTION ENERGIES,STATISTICAL ATOMIC MODELS,SMALL ORGANIC-MOLECULES,AB-INITIO,CHARGE-TRANSFER,INTERMOLECULAR INTERACTIONS,N-ALKANES},
  language     = {eng},
  number       = {1},
  pages        = {161--179},
  title        = {The Monomer Electron Density Force Field (MEDFF) : a physically inspired model for noncovalent interactions},
  url          = {http://dx.doi.org/10.1021/acs.jctc.6b00969},
  volume       = {13},
  year         = {2017},
}

Chicago
Vandenbrande, Steven, Michel Waroquier, Veronique Van Speybroeck, and Toon Verstraelen. 2017. “The Monomer Electron Density Force Field (MEDFF) : a Physically Inspired Model for Noncovalent Interactions.” Journal of Chemical Theory and Computation 13 (1): 161–179.
APA
Vandenbrande, S., Waroquier, M., Van Speybroeck, V., & Verstraelen, T. (2017). The Monomer Electron Density Force Field (MEDFF) : a physically inspired model for noncovalent interactions. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 13(1), 161–179.
Vancouver
1.
Vandenbrande S, Waroquier M, Van Speybroeck V, Verstraelen T. The Monomer Electron Density Force Field (MEDFF) : a physically inspired model for noncovalent interactions. JOURNAL OF CHEMICAL THEORY AND COMPUTATION. 2017;13(1):161–79.
MLA
Vandenbrande, Steven, Michel Waroquier, Veronique Van Speybroeck, et al. “The Monomer Electron Density Force Field (MEDFF) : a Physically Inspired Model for Noncovalent Interactions.” JOURNAL OF CHEMICAL THEORY AND COMPUTATION 13.1 (2017): 161–179. Print.