skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Analytical nuclear gradients for the range-separated many-body dispersion model of noncovalent interactions

Abstract

An accurate treatment of the long-range electron correlation energy, including van der Waals (vdW) or dispersion interactions, is essential for describing the structure, dynamics, and function of a wide variety of systems. Among the most accurate models for including dispersion into density functional theory (DFT) is the range-separated many-body dispersion (MBD) method [A. Ambrosetti et al., J. Chem. Phys., 2014, 140, 18A508], in which the correlation energy is modeled at short-range by a semi-local density functional and at long-range by a model system of coupled quantum harmonic oscillators. In this work, we develop analytical gradients of the MBD energy with respect to nuclear coordinates, including all implicit coordinate dependencies arising from the partitioning of the charge density into Hirshfeld effective volumes. To demonstrate the efficiency and accuracy of these MBD gradients for geometry optimizations of systems with intermolecular and intramolecular interactions, we optimized conformers of the benzene dimer and isolated small peptides with aromatic side-chains. We find excellent agreement with the wavefunction theory reference geometries of these systems (at a fraction of the computational cost) and find that MBD consistently outperforms the popular TS and D3(BJ) dispersion corrections. To demonstrate the performance of the MBD model on a larger systemmore » with supramolecular interactions, we optimized the C 60@C 60H 28 buckyball catcher host–guest complex. In our analysis, we also find that neglecting the implicit nuclear coordinate dependence arising from the charge density partitioning, as has been done in prior numerical treatments, leads to an unacceptable error in the MBD forces, with relative errors of ~20% (on average) that can extend well beyond 100%.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [1]
  1. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
  2. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry; Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology
  3. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry; Princeton Univ., NJ (United States). Princeton Inst. for the Science and Technology of Materials, Dept. of Physics, and Program in Applied and Computational Mathematics
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21)
OSTI Identifier:
1467449
Grant/Contract Number:  
SC0008626
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 3; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES

Citation Formats

Blood-Forsythe, Martin A., Markovich, Thomas, DiStasio, Robert A., Car, Roberto, and Aspuru-Guzik, Alán. Analytical nuclear gradients for the range-separated many-body dispersion model of noncovalent interactions. United States: N. p., 2016. Web. doi:10.1039/c5sc03234b.
Blood-Forsythe, Martin A., Markovich, Thomas, DiStasio, Robert A., Car, Roberto, & Aspuru-Guzik, Alán. Analytical nuclear gradients for the range-separated many-body dispersion model of noncovalent interactions. United States. doi:10.1039/c5sc03234b.
Blood-Forsythe, Martin A., Markovich, Thomas, DiStasio, Robert A., Car, Roberto, and Aspuru-Guzik, Alán. Thu . "Analytical nuclear gradients for the range-separated many-body dispersion model of noncovalent interactions". United States. doi:10.1039/c5sc03234b. https://www.osti.gov/servlets/purl/1467449.
@article{osti_1467449,
title = {Analytical nuclear gradients for the range-separated many-body dispersion model of noncovalent interactions},
author = {Blood-Forsythe, Martin A. and Markovich, Thomas and DiStasio, Robert A. and Car, Roberto and Aspuru-Guzik, Alán},
abstractNote = {An accurate treatment of the long-range electron correlation energy, including van der Waals (vdW) or dispersion interactions, is essential for describing the structure, dynamics, and function of a wide variety of systems. Among the most accurate models for including dispersion into density functional theory (DFT) is the range-separated many-body dispersion (MBD) method [A. Ambrosetti et al., J. Chem. Phys., 2014, 140, 18A508], in which the correlation energy is modeled at short-range by a semi-local density functional and at long-range by a model system of coupled quantum harmonic oscillators. In this work, we develop analytical gradients of the MBD energy with respect to nuclear coordinates, including all implicit coordinate dependencies arising from the partitioning of the charge density into Hirshfeld effective volumes. To demonstrate the efficiency and accuracy of these MBD gradients for geometry optimizations of systems with intermolecular and intramolecular interactions, we optimized conformers of the benzene dimer and isolated small peptides with aromatic side-chains. We find excellent agreement with the wavefunction theory reference geometries of these systems (at a fraction of the computational cost) and find that MBD consistently outperforms the popular TS and D3(BJ) dispersion corrections. To demonstrate the performance of the MBD model on a larger system with supramolecular interactions, we optimized the C60@C60H28 buckyball catcher host–guest complex. In our analysis, we also find that neglecting the implicit nuclear coordinate dependence arising from the charge density partitioning, as has been done in prior numerical treatments, leads to an unacceptable error in the MBD forces, with relative errors of ~20% (on average) that can extend well beyond 100%.},
doi = {10.1039/c5sc03234b},
journal = {Chemical Science},
number = 3,
volume = 7,
place = {United States},
year = {2016},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

van der Waals Volumes and Radii
journal, March 1964

  • Bondi, A.
  • The Journal of Physical Chemistry, Vol. 68, Issue 3, p. 441-451
  • DOI: 10.1021/j100785a001

A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006

  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993