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

Title: Perspective: Ab initio force field methods derived from quantum mechanics

Abstract

It is often desirable to accurately and efficiently model the behavior of large molecular systems in the condensed phase (thousands to tens of thousands of atoms) over long time scales (from nanoseconds to milliseconds). In these cases, ab initio methods are difficult due to the increasing computational cost with the number of electrons. A more computationally attractive alternative is to perform the simulations at the atomic level using a parameterized function to model the electronic energy. Many empirical force fields have been developed for this purpose. However, the functions that are used to model interatomic and intermolecular interactions contain many fitted parameters obtained from selected model systems, and such classical force fields cannot properly simulate important electronic effects. Furthermore, while such force fields are computationally affordable, they are not reliable when applied to systems that differ significantly from those used in their parameterization. They also cannot provide the information necessary to analyze the interactions that occur in the system, making the systematic improvement of the functional forms that are used difficult. Ab initio force field methods aim to combine the merits of both types of methods. The ideal ab initio force fields are built on first principles and require nomore » fitted parameters. Ab initio force field methods surveyed in this perspective are based on fragmentation approaches and intermolecular perturbation theory. This perspective summarizes their theoretical foundation, key components in their formulation, and discusses key aspects of these methods such as accuracy and formal computational cost. The ab initio force fields considered here were developed for different targets, and this perspective also aims to provide a balanced presentation of their strengths and shortcomings. Finally, this perspective suggests some future directions for this actively developing area.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [1]
  1. Ames Lab., and Iowa State Univ., Ames, IA (United States)
  2. Univ. of Colorado, Denver, CO (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); Air Force Research Laboratory (AFRL) - Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC)
OSTI Identifier:
1481785
Alternate Identifier(s):
OSTI ID: 1423723
Grant/Contract Number:  
AC02-06CH11357; AC02-07CH11358
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 9; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Molecular electronic properties; Polarizability; Molecular dynamics; Chemical elements; Ab-initio methods; Intermolecular forces; Perturbation theory; Polarization; Classical force fields; Electrostatics

Citation Formats

Xu, Peng, Guidez, Emilie B., Bertoni, Colleen, and Gordon, Mark S. Perspective: Ab initio force field methods derived from quantum mechanics. United States: N. p., 2018. Web. doi:10.1063/1.5009551.
Xu, Peng, Guidez, Emilie B., Bertoni, Colleen, & Gordon, Mark S. Perspective: Ab initio force field methods derived from quantum mechanics. United States. https://doi.org/10.1063/1.5009551
Xu, Peng, Guidez, Emilie B., Bertoni, Colleen, and Gordon, Mark S. Mon . "Perspective: Ab initio force field methods derived from quantum mechanics". United States. https://doi.org/10.1063/1.5009551. https://www.osti.gov/servlets/purl/1481785.
@article{osti_1481785,
title = {Perspective: Ab initio force field methods derived from quantum mechanics},
author = {Xu, Peng and Guidez, Emilie B. and Bertoni, Colleen and Gordon, Mark S.},
abstractNote = {It is often desirable to accurately and efficiently model the behavior of large molecular systems in the condensed phase (thousands to tens of thousands of atoms) over long time scales (from nanoseconds to milliseconds). In these cases, ab initio methods are difficult due to the increasing computational cost with the number of electrons. A more computationally attractive alternative is to perform the simulations at the atomic level using a parameterized function to model the electronic energy. Many empirical force fields have been developed for this purpose. However, the functions that are used to model interatomic and intermolecular interactions contain many fitted parameters obtained from selected model systems, and such classical force fields cannot properly simulate important electronic effects. Furthermore, while such force fields are computationally affordable, they are not reliable when applied to systems that differ significantly from those used in their parameterization. They also cannot provide the information necessary to analyze the interactions that occur in the system, making the systematic improvement of the functional forms that are used difficult. Ab initio force field methods aim to combine the merits of both types of methods. The ideal ab initio force fields are built on first principles and require no fitted parameters. Ab initio force field methods surveyed in this perspective are based on fragmentation approaches and intermolecular perturbation theory. This perspective summarizes their theoretical foundation, key components in their formulation, and discusses key aspects of these methods such as accuracy and formal computational cost. The ab initio force fields considered here were developed for different targets, and this perspective also aims to provide a balanced presentation of their strengths and shortcomings. Finally, this perspective suggests some future directions for this actively developing area.},
doi = {10.1063/1.5009551},
url = {https://www.osti.gov/biblio/1481785}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 9,
volume = 148,
place = {United States},
year = {2018},
month = {3}
}

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

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Interactions within the alcohol dehydrogenase Zn(II)-metalloenzyme active site: Interplay between subvalence, electron correlation/dispersion, and charge transfer/induction effects
journal, June 2010


Modeling Styrene−Styrene Interactions
journal, January 2006


Development of CHARMM Polarizable Force Field for Nucleic Acid Bases Based on the Classical Drude Oscillator Model
journal, January 2011


Long-range and overlap effects on collision-induced properties
journal, November 1992


Improved Formulas for the Calculation of the Electrostatic Contribution to the Intermolecular Interaction Energy from Multipolar Expansion of the Electronic Distribution
journal, December 2003


Fragment molecular orbital method: use of approximate electrostatic potential
journal, January 2002


Two- and three-body interatomic dispersion energy contributions to binding in molecules and solids
journal, June 2010


UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
journal, December 1992


Charge transfer interaction using quasiatomic minimal-basis orbitals in the effective fragment potential method
journal, November 2013


Ab Initio Atom–Atom Potentials Using C am CASP: Theory and Application to Many-Body Models for the Pyridine Dimer
journal, August 2016


Rapid computation of intermolecular interactions in molecular and ionic clusters: self-consistent polarization plus symmetry-adapted perturbation theory
journal, January 2012


Methanol−Water Mixtures:  A Microsolvation Study Using the Effective Fragment Potential Method
journal, August 2006


Molecular Interactions in Solution: An Overview of Methods Based on Continuous Distributions of the Solvent
journal, November 1994


Ab initio investigation of the aqueous solvation of the nitrate ion
journal, January 2015


Accurate Molecular Crystal Lattice Energies from a Fragment QM/MM Approach with On-the-Fly Ab Initio Force Field Parametrization
journal, October 2011


Unravelling the Origin of Intermolecular Interactions Using Absolutely Localized Molecular Orbitals
journal, September 2007


Multi-state Approach to Chemical Reactivity in Fragment Based Quantum Chemistry Calculations
journal, August 2013


Deviations from Pairwise Additivity in Intermolecular Potentials
journal, December 1967


An effective fragment method for modeling solvent effects in quantum mechanical calculations
journal, August 1996


Derivation of class II force fields. I. Methodology and quantum force field for the alkyl functional group and alkane molecules
journal, February 1994


Intermolecular electrostatic energies using density fitting
journal, July 2005


Extension of the Universal Force Field to Metal–Organic Frameworks
journal, January 2014


Incorporation of a QM/MM Buffer Zone in the Variational Double Self-Consistent Field Method
journal, November 2008


Energy decomposition analysis of covalent bonds and intermolecular interactions
journal, July 2009


Physically-Motivated Force Fields from Symmetry-Adapted Perturbation Theory
journal, February 2013


Energy-Based Molecular Fragmentation Methods
journal, April 2015


CHARMM fluctuating charge force field for proteins: II Protein/solvent properties from molecular dynamics simulations using a nonadditive electrostatic model
journal, January 2004


Benzene−Pyridine Interactions Predicted by the Effective Fragment Potential Method
journal, May 2011


Interaction of neutral and zwitterionic glycine with Zn2+ in gas phase:ab initio and SIBFA molecular mechanics calculations
journal, January 2000


Distributed multipole analysis: Methods and applications
journal, December 1985


Ab initio quality one-electron properties of large molecules: Development and testing of molecular tailoring approach
journal, February 2003


Charge transfer interaction in the effective fragment potential method
journal, June 2006


Surface Affinity of the Hydronium Ion: The Effective Fragment Potential and Umbrella Sampling
journal, December 2014


Parametrizing a polarizable force field from ab initio data. I. The fluctuating point charge model
journal, January 1999


S/G-1: An ab Initio Force-Field Blending Frozen Hermite Gaussian Densities and Distributed Multipoles. Proof of Concept and First Applications to Metal Cations
journal, June 2014


Strike a balance: Optimization of backbone torsion parameters of AMBER polarizable force field for simulations of proteins and peptides
journal, January 2006


Particle mesh Ewald: An N ⋅log( N ) method for Ewald sums in large systems
journal, June 1993


LIBEFP: A new parallel implementation of the effective fragment potential method as a portable software library
journal, July 2013


The relaxation of molecular crystal structures using a distributed multipole electrostatic model
journal, May 1995


Empirical energy functions for energy minimization and dynamics of nucleic acids
journal, October 1986


Polarizable Atomic Multipole-Based AMOEBA Force Field for Proteins
journal, August 2013


Truncated Conjugate Gradient: An Optimal Strategy for the Analytical Evaluation of the Many-Body Polarization Energy and Forces in Molecular Simulations
journal, December 2016


Transferable Next-Generation Force Fields from Simple Liquids to Complex Materials
journal, February 2015


Towards a force field based on density fitting
journal, March 2006


Nonequilibrium solvation: An ab initio quantum‐mechanical method in the continuum cavity model approximation
journal, May 1993


The OPLS [optimized potentials for liquid simulations] potential functions for proteins, energy minimizations for crystals of cyclic peptides and crambin
journal, March 1988


What Governs the Proton Ordering in Ice XV?
journal, September 2013


Derivation of Class II Force Fields. 2. Derivation and Characterization of a Class II Force Field, CFF93, for the Alkyl Functional Group and Alkane Molecules
journal, March 1994


Intermolecular interactions: Reproduction of the results of ab initio supermolecule computations by an additive procedure
journal, March 1979


Fragmentation Methods: A Route to Accurate Calculations on Large Systems
journal, August 2011


An improved simple model for the van der Waals potential based on universal damping functions for the dispersion coefficients
journal, April 1984


Dispersion Interactions in QM/EFP
journal, December 2017


Molecular fractionation with conjugate caps for full quantum mechanical calculation of protein–molecule interaction energy
journal, August 2003


AMBER: Assisted model building with energy refinement. A general program for modeling molecules and their interactions
journal, October 1981


Spatially Homogeneous QM/MM for Systems of Interacting Molecules with on-the-Fly ab Initio Force-Field Parametrization
journal, December 2009


An all atom force field for simulations of proteins and nucleic acids: An All Atom Force Field
journal, April 1986


Modeling Polymorphic Molecular Crystals with Electronic Structure Theory
journal, March 2016


Modeling intermolecular exchange integrals between nonorthogonal molecular orbitals
journal, May 1996


Theoretical method for full ab initio calculation of DNA/RNA–ligand interaction energy
journal, June 2004


Polarizable Force Fields:  History, Test Cases, and Prospects
journal, September 2007


Interaction of the van der Waals Type Between Three Atoms
journal, June 1943


Effective Fragment Molecular Orbital Method: A Merger of the Effective Fragment Potential and Fragment Molecular Orbital Methods
journal, August 2010


Derivation and Implementation of the Gradient of the R –7 Dispersion Interaction in the Effective Fragment Potential Method
journal, January 2016


Accuracy and efficiency of electronic energies from systematic molecular fragmentation
journal, September 2006


The fast Fourier Poisson method for calculating Ewald sums
journal, August 1994


An integrated effective fragment—polarizable continuum approach to solvation: Theory and application to glycine
journal, January 2002


Atom–atom potentials from ab initio calculations
journal, January 2007


Modeling Copper(I) Complexes:  SIBFA Molecular Mechanics versus ab Initio Energetics and Geometrical Arrangements
journal, June 2002


Alanine: Then There Was Water
journal, June 2009


Molecular mechanics. The MM3 force field for hydrocarbons. 1
journal, November 1989


CHARMM fluctuating charge force field for proteins: I parameterization and application to bulk organic liquid simulations
journal, January 2003


Importance of Three-Body Interactions in Molecular Dynamics Simulations of Water Demonstrated with the Fragment Molecular Orbital Method
journal, March 2016


Molecular mechanics. The MM3 force field for hydrocarbons. 2. Vibrational frequencies and thermodynamics
journal, November 1989


A General Quantum Mechanically Derived Force Field (QMDFF) for Molecules and Condensed Phase Simulations
journal, September 2014


Specificity of Acyl Transfer from 2-Mercaptobenzamide Thioesters to the HIV-1 Nucleocapsid Protein
journal, September 2007


Molecular mechanics. The MM3 force field for hydrocarbons. 3. The van der Waals' potentials and crystal data for aliphatic and aromatic hydrocarbons
journal, November 1989


Design of a Next Generation Force Field:  The X-POL Potential
journal, August 2007


Molecular Tailoring Approach for Simulation of Electrostatic Properties
journal, September 1994


Frozen fragment reduced variational space analysis of hydrogen bonding interactions. Application to the water dimer
journal, August 1987


Beyond Born–Mayer: Improved Models for Short-Range Repulsion in ab Initio Force Fields
journal, July 2016


Toward accurate solvation dynamics of lanthanides and actinides in water using polarizable force fields: from gas-phase energetics to hydration free energies
journal, March 2012


The dispersion interaction between quantum mechanics and effective fragment potential molecules
journal, June 2012


A study of water clusters using the effective fragment potential and Monte Carlo simulated annealing
journal, February 2000


Accurate treatment of nonbonded interactions within systematic molecular fragmentation
journal, January 2009


A general intermolecular force field based on tight-binding quantum chemical calculations
journal, October 2017


Generalization of the Gaussian electrostatic model: Extension to arbitrary angular momentum, distributed multipoles, and speedup with reciprocal space methods
journal, November 2006


Modeling of inhibitor–metalloenzyme interactions and selectivity using molecular mechanics grounded in quantum chemistry
journal, April 1998


Density functional theory based effective fragment potential method
journal, April 2003


The exact multicenter multipolar part of a molecular charge distribution and its simplified representations
journal, April 1988


Multipole Moments in the Effective Fragment Potential Method
journal, February 2017


Energy decomposition analysis of intermolecular interactions using a block-localized wave function approach
journal, April 2000


Practical quantum mechanics-based fragment methods for predicting molecular crystal properties
journal, January 2012


Adjustment of the SIBFA method for potential maps to study hydrogen bonding vibrational frequencies
journal, January 1991


Analytic Gradients for the Effective Fragment Molecular Orbital Method
journal, September 2016


Optimized intermolecular potential functions for amides and peptides. Structure and properties of liquid amides
journal, February 1985


Fully Integrated Effective Fragment Molecular Orbital Method
journal, April 2013


Predicting Organic Crystal Lattice Energies with Chemical Accuracy
journal, December 2010


A new analysis of charge transfer and polarization for ligand–metal bonding: Model studies of Al 4 CO and Al 4 NH 3
journal, May 1984


First-Principles Many-Body Force Fields from the Gas Phase to Liquid: A “Universal” Approach
journal, April 2014


Approximate ab initio energies by systematic molecular fragmentation
journal, April 2005


Water−Benzene Interactions: An Effective Fragment Potential and Correlated Quantum Chemistry Study
journal, March 2009


Cation-ligand interactions: Reproduction of extended basis set Ab initio SCF computations by the SIBFA 2 additive procedure
journal, December 1985


The three-body fragment molecular orbital method for accurate calculations of large systems
journal, December 2006


The Effective Fragment Potential Method:  A QM-Based MM Approach to Modeling Environmental Effects in Chemistry
journal, January 2001


Exploiting space-group symmetry in fragment-based molecular crystal calculations
journal, October 2014


Gradients of the polarization energy in the effective fragment potential method
journal, November 2006


Accurate First Principles Model Potentials for Intermolecular Interactions
journal, April 2013


Continuum solvation of large molecules described by QM/MM: a semi-iterative implementation of the PCM/EFP interface
journal, March 2003


Accidental Degeneracy in Crystalline Aspirin: New Insights from High-Level ab Initio Calculations
journal, April 2012


A new force field for molecular mechanical simulation of nucleic acids and proteins
journal, February 1984


Polarizable force fields
journal, April 2001


Effective Fragment Potential Study of the Interaction of DNA Bases
journal, October 2011


GEM*: A Molecular Electronic Density-Based Force Field for Molecular Dynamics Simulations
journal, March 2014


CHARMM: A program for macromolecular energy, minimization, and dynamics calculations
journal, July 1983


A combined discrete/continuum solvation model: Application to glycine
journal, July 2000


Energy decomposition analysis approaches and their evaluation on prototypical protein–drug interaction patterns
journal, January 2015


The R –7 Dispersion Interaction in the General Effective Fragment Potential Method
journal, March 2014


The MM3 force field for amides, polypeptides and proteins
journal, March 1991


A smooth particle mesh Ewald method
journal, November 1995


Efficient and Accurate Fragmentation Methods
journal, May 2014


Intermolecular interactions: Elaboration on an additive procedure including an explicit charge-transfer contribution
journal, January 1986


Fragment molecular orbital method: an approximate computational method for large molecules
journal, November 1999


Damping functions in the effective fragment potential method
journal, April 2009


Benchmark database of accurate (MP2 and CCSD(T) complete basis set limit) interaction energies of small model complexes, DNA base pairs, and amino acid pairs
journal, January 2006


Modeling π–π Interactions with the Effective Fragment Potential Method: The Benzene Dimer and Substituents
journal, June 2008


Electrostatic interaction of a solute with a continuum. Improved description of the cavity and of the surface cavity bound charge distribution.
journal, September 1987


Adjustment of the SIBFA Method for Potential Maps to Study Hydrogen Bonding Vibrational Frequencies
conference, January 1991


    Works referencing / citing this record:

    Multiscale modelling of photoinduced processes in composite systems
    journal, April 2019


    Could Quantum Mechanical Properties Be Reflected on Classical Molecular Dynamics? The Case of Halogenated Organic Compounds of Biological Interest
    journal, December 2019