Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Reactive Monte Carlo sampling with an ab initio potential

Abstract

Here, we present the first application of reactive Monte Carlo in a first-principles context. The algorithm samples in a modified NVT ensemble in which the volume, temperature, and total number of atoms of a given type are held fixed, but molecular composition is allowed to evolve through stochastic variation of chemical connectivity. We also discuss general features of the method, as well as techniques needed to enhance the efficiency of Boltzmann sampling. Finally, we compare the results of simulation of NH3 to those of ab initio molecular dynamics (AIMD). Furthermore, we find that there are regions of state space for which RxMC sampling is much more efficient than AIMD due to the “rare-event” character of chemical reactions.

Authors:
 [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1340916
Alternate Identifier(s):
OSTI ID: 1250976
Report Number(s):
LA-UR-16-21006
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC52-06NA25396; LA-UR-16-21006
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 17; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
97 MATHEMATICS AND COMPUTING; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Leiding, Jeff, and Coe, Joshua D. Reactive Monte Carlo sampling with an ab initio potential. United States: N. p., 2016. Web. doi:10.1063/1.4948303.
Copy to clipboard
Leiding, Jeff, & Coe, Joshua D. Reactive Monte Carlo sampling with an ab initio potential. United States. https://doi.org/10.1063/1.4948303
Copy to clipboard
Leiding, Jeff, and Coe, Joshua D. Wed . "Reactive Monte Carlo sampling with an ab initio potential". United States. https://doi.org/10.1063/1.4948303. https://www.osti.gov/servlets/purl/1340916.
Copy to clipboard
@article{osti_1340916,
title = {Reactive Monte Carlo sampling with an ab initio potential},
author = {Leiding, Jeff and Coe, Joshua D.},
abstractNote = {Here, we present the first application of reactive Monte Carlo in a first-principles context. The algorithm samples in a modified NVT ensemble in which the volume, temperature, and total number of atoms of a given type are held fixed, but molecular composition is allowed to evolve through stochastic variation of chemical connectivity. We also discuss general features of the method, as well as techniques needed to enhance the efficiency of Boltzmann sampling. Finally, we compare the results of simulation of NH3 to those of ab initio molecular dynamics (AIMD). Furthermore, we find that there are regions of state space for which RxMC sampling is much more efficient than AIMD due to the “rare-event” character of chemical reactions.},
doi = {10.1063/1.4948303},
journal = {Journal of Chemical Physics},
number = 17,
volume = 144,
place = {United States},
year = {Wed May 04 00:00:00 EDT 2016},
month = {Wed May 04 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.4948303
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

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

Microscopic Approaches to Liquid Nitromethane Detonation Properties
journal, April 2008

  • Hervouët, Anaïs; Desbiens, Nicolas; Bourasseau, Emeric
  • The Journal of Physical Chemistry B, Vol. 112, Issue 16
  • DOI: 10.1021/jp077250n

Monte Carlo Simulation of Equilibrium Reactions at Vapor−Liquid Interfaces
journal, December 2005

  • Turner, C. Heath
  • The Journal of Physical Chemistry B, Vol. 109, Issue 49
  • DOI: 10.1021/jp0528156

The Interior Structure, Composition, and Evolution of Giant Planets
journal, December 2009

Hybrid Monte Carlo
journal, September 1987

Increasing the efficiency of Monte Carlo simulation with sampling from an approximate potential
journal, January 2013

Projector augmented-wave method
journal, December 1994

Amino wagging and inversion in hydrazines
journal, August 1974

Monte Carlo adiabatic simulation of equilibrium reacting systems: The ammonia synthesis reaction
journal, August 2005

Vapor–Liquid Coexistence Curves for Methanol and Methane Using Dispersion-Corrected Density Functional Theory
journal, October 2011

  • McGrath, Matthew J.; Kuo, I. -F. Will; Ghogomu, Julius N.
  • The Journal of Physical Chemistry B, Vol. 115, Issue 40
  • DOI: 10.1021/jp205072v

An efficient approach to ab initio Monte Carlo simulation
journal, January 2014

  • Leiding, Jeff; Coe, Joshua D.
  • The Journal of Chemical Physics, Vol. 140, Issue 3
  • DOI: 10.1063/1.4855755

The reaction ensemble method for the computer simulation of chemical and phase equilibria. I. Theory and basic examples
journal, February 1994

  • Smith, W. R.; Triska, B.
  • The Journal of Chemical Physics, Vol. 100, Issue 4
  • DOI: 10.1063/1.466443

Using a classical potential as an efficient importance function for sampling from an ab initio potential
journal, January 2000

  • Iftimie, Radu; Salahub, Dennis; Wei, Dongqing
  • The Journal of Chemical Physics, Vol. 113, Issue 12
  • DOI: 10.1063/1.1289534

Microscopic Calculations of Hugoniot Curves of Neat Triaminotrinitrobenzene (TATB) and of Its Detonation Products
journal, October 2011

  • Bourasseau, Emeric; Maillet, Jean-Bernard; Desbiens, Nicolas
  • The Journal of Physical Chemistry A, Vol. 115, Issue 39
  • DOI: 10.1021/jp2047739

Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes
journal, March 1977

  • Ryckaert, Jean-Paul; Ciccotti, Giovanni; Berendsen, Herman J. C.
  • Journal of Computational Physics, Vol. 23, Issue 3
  • DOI: 10.1016/0021-9991(77)90098-5

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

Isothermal–isobaric Monte Carlo simulations of liquid lithium using density functional theory
journal, January 2006

Density functional study of chemical reaction equilibrium for dimerization reactions in slit and cylindrical nanopores
journal, April 2009

  • Malijevský, Alexandr; Lísal, Martin
  • The Journal of Chemical Physics, Vol. 130, Issue 16
  • DOI: 10.1063/1.3125925

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Strict detailed balance is unnecessary in Monte Carlo simulation
journal, February 1999

  • Manousiouthakis, Vasilios I.; Deem, Michael W.
  • The Journal of Chemical Physics, Vol. 110, Issue 6
  • DOI: 10.1063/1.477973

Development of the ReaxFF Reactive Force Field for Describing Transition Metal Catalyzed Reactions, with Application to the Initial Stages of the Catalytic Formation of Carbon Nanotubes
journal, January 2005

  • Nielson, Kevin D.; van Duin, Adri C. T.; Oxgaard, Jonas
  • The Journal of Physical Chemistry A, Vol. 109, Issue 3
  • DOI: 10.1021/jp046244d

Reaction Mechanism of N 2 /H 2 Conversion to NH 3 :  A Theoretical Study
journal, April 2003

  • Hwang, Der-Yan; Mebel, Alexander M.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 16
  • DOI: 10.1021/jp0270349

Equation of state and phase diagram of ammonia at high pressures from ab initio simulations
journal, June 2013

  • Bethkenhagen, Mandy; French, Martin; Redmer, Ronald
  • The Journal of Chemical Physics, Vol. 138, Issue 23
  • DOI: 10.1063/1.4810883

Self-consistent-charge density-functional tight-binding method for simulations of complex materials properties
journal, September 1998

  • Elstner, M.; Porezag, D.; Jungnickel, G.
  • Physical Review B, Vol. 58, Issue 11, p. 7260-7268
  • DOI: 10.1103/PhysRevB.58.7260

Does solvent density play a role in the keto–enol tautomerism of acetylacetone?
journal, April 2006

Optimal sampling efficiency in Monte Carlo simulation with an approximate potential
journal, April 2009

  • Coe, Joshua D.; Sewell, Thomas D.; Shaw, M. Sam
  • The Journal of Chemical Physics, Vol. 130, Issue 16
  • DOI: 10.1063/1.3116788

Extending the Time Scale in Atomistic Simulation of Materials
journal, August 2002

Efficient determination of Hugoniot states using classical molecular simulation techniques
journal, November 2003

Empirical potential for hydrocarbons for use in simulating the chemical vapor deposition of diamond films
journal, November 1990

Molecular simulations of Hugoniots of detonation product mixtures at chemical equilibrium: Microscopic calculation of the Chapman-Jouguet state
journal, August 2007

  • Bourasseau, Emeric; Dubois, Vincent; Desbiens, Nicolas
  • The Journal of Chemical Physics, Vol. 127, Issue 8
  • DOI: 10.1063/1.2766939

Monte Carlo simulation of equilibrium chemical composition of molecular fluid mixtures in the N atoms PT ensemble
journal, June 1991

  • Shaw, M. S.
  • The Journal of Chemical Physics, Vol. 94, Issue 11
  • DOI: 10.1063/1.460188

Ab initiomolecular dynamics for liquid metals
journal, January 1993

Chemical equilibrium in high pressure molecular fluid mixtures
conference, January 1994

  • Shaw, M. S.
  • High-pressure science and technology—1993, AIP Conference Proceedings
  • DOI: 10.1063/1.46419

Equation of State Calculations by Fast Computing Machines
journal, June 1953

  • Metropolis, Nicholas; Rosenbluth, Arianna W.; Rosenbluth, Marshall N.
  • The Journal of Chemical Physics, Vol. 21, Issue 6
  • DOI: 10.1063/1.1699114

Toward a Monte Carlo program for simulating vapor–liquid phase equilibria from first principles
journal, July 2005

  • McGrath, Matthew J.; Siepmann, J. Ilja; Kuo, I-Feng W.
  • Computer Physics Communications, Vol. 169, Issue 1-3
  • DOI: 10.1016/j.cpc.2005.03.065

A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

  • Nosé, Shuichi
  • The Journal of Chemical Physics, Vol. 81, Issue 1
  • DOI: 10.1063/1.447334

Nested Markov chain Monte Carlo sampling of a density functional theory potential: Equilibrium thermodynamics of dense fluid nitrogen
journal, August 2009

  • Coe, Joshua D.; Sewell, Thomas D.; Shaw, M. Sam
  • The Journal of Chemical Physics, Vol. 131, Issue 7
  • DOI: 10.1063/1.3200904

Simulating Fluid-Phase Equilibria of Water from First Principles †
journal, January 2006

  • McGrath, Matthew J.; Siepmann, J. Ilja; Kuo, I-Feng W.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 2
  • DOI: 10.1021/jp0535947

Calculation of the Gibbs free energy of solvation and dissociation of HCl in water via Monte Carlo simulations and continuum solvation models
journal, January 2013

  • McGrath, Matthew J.; Kuo, I-F. Will; Ngouana W., Brice F.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 32
  • DOI: 10.1039/c3cp51762d

Assessment of Two Surface Monte Carlo (TSMC) method to find stationary points of (H2O)15 and (H2O)20 clusters
journal, May 2007

Reactive Monte Carlo and grand-canonical Monte Carlo simulations of the propene metathesis reaction system
journal, April 2005

  • Hansen, Niels; Jakobtorweihen, Sven; Keil, Frerich J.
  • The Journal of Chemical Physics, Vol. 122, Issue 16
  • DOI: 10.1063/1.1884108

Efficient sampling for ab initio Monte Carlo simulation of molecular clusters using an interpolated potential energy surface
journal, January 2009

  • Nakayama, Akira; Seki, Nanami; Taketsugu, Tetsuya
  • The Journal of Chemical Physics, Vol. 130, Issue 2
  • DOI: 10.1063/1.3055910

A new algorithm for Monte Carlo simulation of Ising spin systems
journal, January 1975

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Simulation of chemical reaction equilibria and kinetics in heterogeneous carbon micropores
journal, August 2002

Extended Lagrangian Born-Oppenheimer molecular dynamics simulations of the shock-induced chemistry of phenylacetylene
journal, February 2015

  • Cawkwell, M. J.; Niklasson, Anders M. N.; Dattelbaum, Dana M.
  • The Journal of Chemical Physics, Vol. 142, Issue 6
  • DOI: 10.1063/1.4907909

Liquid Water from First Principles:  Investigation of Different Sampling Approaches
journal, August 2004

  • Kuo, I-Feng W.; Mundy, Christopher J.; McGrath, Matthew J.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 34
  • DOI: 10.1021/jp047788i

First principles Monte Carlo simulations of aggregation in the vapor phase of hydrogen fluoride
journal, January 2010

  • McGrath, Matthew J.; Ghogomu, Julius. N.; Mundy, Christopher J.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 27
  • DOI: 10.1039/b924506e

Simplified LCAO Method for the Periodic Potential Problem
journal, June 1954

A Hybrid Monte Carlo Method for Equilibrium Equation of State of Detonation Products
conference, January 2002

  • Shaw, M. Sam
  • Shock Compression of Condensed Matter - 2001: 12th APS Topical Conference, AIP Conference Proceedings
  • DOI: 10.1063/1.1483505

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

The reaction ensemble method for the computer simulation of chemical and phase equilibria. II. The Br2+Cl2+BrCl system
journal, May 1999

  • Lı́sal, Martin; Nezbeda, Ivo; Smith, William R.
  • The Journal of Chemical Physics, Vol. 110, Issue 17
  • DOI: 10.1063/1.478767

Ab initio simulations of hot dense methane during shock experiments
journal, December 2012

  • Sherman, Benjamin L.; Wilson, Hugh F.; Weeraratne, Dayanthie
  • Physical Review B, Vol. 86, Issue 22
  • DOI: 10.1103/PhysRevB.86.224113

Influence of chemical and physical surface heterogeneity on chemical reaction equilibria in carbon micropores
journal, December 2001

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994

ReaxFF:  A Reactive Force Field for Hydrocarbons
journal, October 2001

  • van Duin, Adri C. T.; Dasgupta, Siddharth; Lorant, Francois
  • The Journal of Physical Chemistry A, Vol. 105, Issue 41
  • DOI: 10.1021/jp004368u

Monte Carlo Simulation of Equilibrium Reactions at Modified Vapor−Liquid Interfaces
journal, February 2007

Molecular simulation of shocked materials using the reactive Monte Carlo method
journal, August 2002

Theoretical advances in the dissolution studies of mineral–water interfaces
journal, June 2010

Interior Structure of Neptune: Comparison with Uranus
journal, August 1991

Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985

Simulation of chemical reaction equilibria by the reaction ensemble Monte Carlo method: a review†
journal, February 2008

Molecular simulation of multicomponent reaction and phase equilibria in MTBE ternary system
journal, April 2000

  • Lísal, Martin; Smith, William R.; Nezbeda, Ivo
  • AIChE Journal, Vol. 46, Issue 4
  • DOI: 10.1002/aic.690460419

Mean-Value Point in the Brillouin Zone
journal, June 1973

Simulating the Reactions of CO 2 in Aqueous Monoethanolamine Solution by Reaction Ensemble Monte Carlo Using the Continuous Fractional Component Method
journal, May 2015

  • Balaji, Sayee Prasaad; Gangarapu, Satesh; Ramdin, Mahinder
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 6
  • DOI: 10.1021/acs.jctc.5b00160

Re-examining the properties of the aqueous vapor–liquid interface using dispersion corrected density functional theory
journal, September 2011

  • Baer, Marcel D.; Mundy, Christopher J.; McGrath, Matthew J.
  • The Journal of Chemical Physics, Vol. 135, Issue 12
  • DOI: 10.1063/1.3633239

Cavity-bias sampling in reaction ensemble Monte Carlo simulations
journal, October 2005

Replica Exchange for Reactive Monte Carlo Simulations †
journal, November 2007

  • Turner, C. Heath; Brennan, John K.; Lísal, Martin
  • The Journal of Physical Chemistry C, Vol. 111, Issue 43
  • DOI: 10.1021/jp072655t

Hybrid Monte Carlo method for condensed-matter systems
journal, January 1992

Effect of confinement on chemical reaction equilibria: The reactions 2NO⇔(NO)2 and N2+3H2⇔2NH3 in carbon micropores
journal, January 2001

  • Turner, C. Heath; Johnson, J. Karl; Gubbins, Keith E.
  • The Journal of Chemical Physics, Vol. 114, Issue 4
  • DOI: 10.1063/1.1328756

Tight-binding models and density-functional theory
journal, June 1989

A general method for numerically simulating the stochastic time evolution of coupled chemical reactions
journal, December 1976

Reactive canonical Monte Carlo: A new simulation technique for reacting or associating fluids
journal, February 1994

  • Johnson, J. Karl; Panagiotopoulos, Athanassios Z.; Gubbins, Keith E.
  • Molecular Physics, Vol. 81, Issue 3
  • DOI: 10.1080/00268979400100481

Monte Carlo simulations using sampling from an approximate potential
journal, May 2003

  • Gelb, Lev D.
  • The Journal of Chemical Physics, Vol. 118, Issue 17
  • DOI: 10.1063/1.1563597

Isobaric-Isothermal Monte Carlo Simulations from First Principles: Application to Liquid Water at Ambient Conditions
journal, September 2005

  • McGrath, Matthew J.; Siepmann, J. Ilja; Kuo, I-Feng W.
  • ChemPhysChem, Vol. 6, Issue 9
  • DOI: 10.1002/cphc.200400580

Vapor–liquid equilibria of water from first principles: comparison of density functionals and basis sets
journal, November 2006

Density functional theory guided Monte Carlo simulations: Application to melting of Na 13
journal, February 2012

  • Bulusu, Satya; Fournier, René
  • The Journal of Chemical Physics, Vol. 136, Issue 6
  • DOI: 10.1063/1.3684628
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Towards operando computational modeling in heterogeneous catalysis
    journal, January 2018

    • Grajciar, Lukáš; Heard, Christopher J.; Bondarenko, Anton A.
    • Chemical Society Reviews, Vol. 47, Issue 22
    • DOI: 10.1039/c8cs00398j

    Equations of state for polyethylene and its shock-driven decomposition products
    journal, July 2019

    • Maerzke, Katie A.; Coe, Joshua D.; Ticknor, Christopher
    • Journal of Applied Physics, Vol. 126, Issue 4
    • DOI: 10.1063/1.5099371

    Towards operando computational modeling in heterogeneous catalysis
    journal, January 2018

    • Grajciar, Lukáš; Heard, Christopher J.; Bondarenko, Anton A.
    • Chemical Society Reviews, Vol. 47, Issue 22
    • DOI: 10.1039/c8cs00398j

    Direct coupling of first-principles calculations with replica exchange Monte Carlo sampling of ion disorder in solids
    journal, January 2019

    • Kasamatsu, Shusuke; Sugino, Osamu
    • Journal of Physics: Condensed Matter, Vol. 31, Issue 8
    • DOI: 10.1088/1361-648x/aaf75c

    Molecular Simulation of Chemical Reaction Equilibrium by Computationally Efficient Free Energy Minimization
    journal, August 2018

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: