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

Title: Evaluating Thermal Corrections for Adsorption Processes at the Metal/Gas Interface

Abstract

Adsorption and desorption steps are key for active catalysts and rely on a subtle balance between enthalpic and entropic terms. Although the enthalpic term is becoming ever more accurate through density functional development, the entropic term remains underrated and its precise determination a great challenge. In this work, we have performed extensive first principles thermodynamic integration (TI) simulations for the adsorption of small (e.g., CO) to larger (e.g., phenol) molecules at metallic surfaces and compared their adsorption free energies to the values obtained by vertical, static statistical mechanics approximations to thermal corrections invoking three different approximations for the low-frequency modes. We have found an excellent agreement between the vertical corrections and the TI for minima, for both weakly bound systems (e.g. CO2 and formic acid) and strongly chemisorbed molecules such as phenol or CO. While the treatment of the low-frequency modes has a minor impact on the agreement with TI, all vertical corrections systematically overestimate activation energies by 0.1-0.2 eV compared to TI, demonstrating a noticeable lowering of activation barriers. As an effect of this study, we suggest that the vertical corrections and in particular the standard harmonic approximation can be safely applied to chemisorption minima, while the activation energiesmore » are likely to be overestimated. Hence, if a greater accuracy than ~0.2 eV is required for activation free energies, we recommend to use thermodynamic integration, which for small to medium-sized molecules in gas phase is accessible with a reasonable computational effort, but requires a dense sampling in the transition state region.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Claude Bernard Univ. Lyon 1 (France)
  2. Univ. of Burgundy-Franche-Comté (France)
  3. Univ. of California, Los Angeles, CA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Harvard Univ., Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); French National Research Agency
OSTI Identifier:
1595613
Grant/Contract Number:  
SC0012573
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 47; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Réocreux, Romain, Michel, Carine, Fleurat-Lessard, Paul, Sautet, Philippe, and Steinmann, Stephan N. Evaluating Thermal Corrections for Adsorption Processes at the Metal/Gas Interface. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.9b09863.
Copy to clipboard
Réocreux, Romain, Michel, Carine, Fleurat-Lessard, Paul, Sautet, Philippe, & Steinmann, Stephan N. Evaluating Thermal Corrections for Adsorption Processes at the Metal/Gas Interface. United States. https://doi.org/10.1021/acs.jpcc.9b09863
Copy to clipboard
Réocreux, Romain, Michel, Carine, Fleurat-Lessard, Paul, Sautet, Philippe, and Steinmann, Stephan N. Wed . "Evaluating Thermal Corrections for Adsorption Processes at the Metal/Gas Interface". United States. https://doi.org/10.1021/acs.jpcc.9b09863. https://www.osti.gov/servlets/purl/1595613.
Copy to clipboard
@article{osti_1595613,
title = {Evaluating Thermal Corrections for Adsorption Processes at the Metal/Gas Interface},
author = {Réocreux, Romain and Michel, Carine and Fleurat-Lessard, Paul and Sautet, Philippe and Steinmann, Stephan N.},
abstractNote = {Adsorption and desorption steps are key for active catalysts and rely on a subtle balance between enthalpic and entropic terms. Although the enthalpic term is becoming ever more accurate through density functional development, the entropic term remains underrated and its precise determination a great challenge. In this work, we have performed extensive first principles thermodynamic integration (TI) simulations for the adsorption of small (e.g., CO) to larger (e.g., phenol) molecules at metallic surfaces and compared their adsorption free energies to the values obtained by vertical, static statistical mechanics approximations to thermal corrections invoking three different approximations for the low-frequency modes. We have found an excellent agreement between the vertical corrections and the TI for minima, for both weakly bound systems (e.g. CO2 and formic acid) and strongly chemisorbed molecules such as phenol or CO. While the treatment of the low-frequency modes has a minor impact on the agreement with TI, all vertical corrections systematically overestimate activation energies by 0.1-0.2 eV compared to TI, demonstrating a noticeable lowering of activation barriers. As an effect of this study, we suggest that the vertical corrections and in particular the standard harmonic approximation can be safely applied to chemisorption minima, while the activation energies are likely to be overestimated. Hence, if a greater accuracy than ~0.2 eV is required for activation free energies, we recommend to use thermodynamic integration, which for small to medium-sized molecules in gas phase is accessible with a reasonable computational effort, but requires a dense sampling in the transition state region.},
doi = {10.1021/acs.jpcc.9b09863},
journal = {Journal of Physical Chemistry. C},
number = 47,
volume = 123,
place = {United States},
year = {Wed Oct 30 00:00:00 EDT 2019},
month = {Wed Oct 30 00:00:00 EDT 2019}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.9b09863
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 16 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:

Understanding the Optimal Adsorption Energies for Catalyst Screening in Heterogeneous Catalysis
journal, December 2013

  • Yang, Bo; Burch, Robbie; Hardacre, Christopher
  • ACS Catalysis, Vol. 4, Issue 1
  • DOI: 10.1021/cs400727f

Controlling the Adsorption of Aromatic Compounds on Pt(111) with Oxygenate Substituents: From DFT to Simple Molecular Descriptors
journal, May 2016

  • Réocreux, Romain; Huynh, Minh; Michel, Carine
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 11
  • DOI: 10.1021/acs.jpclett.6b00612

Catalytic Hydrogenation of Unsaturated Aldehydes on Pt(111): Understanding the Selectivity from First-Principles Calculations
journal, August 2005

  • Loffreda, David; Delbecq, Françoise; Vigné, Fabienne
  • Angewandte Chemie International Edition, Vol. 44, Issue 33
  • DOI: 10.1002/anie.200500913

Unsupported shaped cobalt nanoparticles as efficient and recyclable catalysts for the solvent-free acceptorless dehydrogenation of alcohols
journal, January 2018

  • Viola, Arnaud; Peron, Jennifer; Kazmierczak, Kamila
  • Catalysis Science & Technology, Vol. 8, Issue 2
  • DOI: 10.1039/C7CY02089A

The Pressure Gap for Thiols: Methanethiol Self-Assembly on Au(111) from Vacuum to 1 bar
journal, April 2019

  • Mom, Rik V.; Melissen, Sigismund T. A. G.; Sautet, Philippe
  • The Journal of Physical Chemistry C, Vol. 123, Issue 19
  • DOI: 10.1021/acs.jpcc.9b03045

E LECTRONIC S TRUCTURE AND C ATALYSIS ON M ETAL S URFACES
journal, October 2002

Chemical accuracy for the van der Waals density functional
journal, December 2009

  • Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
  • Journal of Physics: Condensed Matter, Vol. 22, Issue 2
  • DOI: 10.1088/0953-8984/22/2/022201

Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012

Molecular adsorption at Pt(111). How accurate are DFT functionals?
journal, January 2015

  • Gautier, Sarah; Steinmann, Stephan N.; Michel, Carine
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 43
  • DOI: 10.1039/C5CP04534G

Validation of Density Functionals for Adsorption Energies on Transition Metal Surfaces
journal, January 2017

  • Duanmu, Kaining; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 2
  • DOI: 10.1021/acs.jctc.6b01156

DFT-Based Method for More Accurate Adsorption Energies: An Adaptive Sum of Energies from RPBE and vdW Density Functionals
journal, February 2017

  • Hensley, Alyssa J. R.; Ghale, Kushal; Rieg, Carolin
  • The Journal of Physical Chemistry C, Vol. 121, Issue 9
  • DOI: 10.1021/acs.jpcc.6b10187

Single crystal adsorption microcalorimetry
journal, September 1991

A novel single-crystal adsorption calorimeter and additions for determining metal adsorption and adhesion energies
journal, June 1998

  • Stuckless, J. T.; Frei, Nathan A.; Campbell, Charles T.
  • Review of Scientific Instruments, Vol. 69, Issue 6
  • DOI: 10.1063/1.1148971

The Entropies of Adsorbed Molecules
journal, October 2012

  • Campbell, Charles T.; Sellers, Jason R. V.
  • Journal of the American Chemical Society, Vol. 134, Issue 43
  • DOI: 10.1021/ja3080117

Thermal desorption of gases
journal, July 1962

Decomposition Mechanism of Anisole on Pt(111): Combining Single-Crystal Experiments and First-Principles Calculations
journal, November 2016

  • Réocreux, Romain; Ould Hamou, Cherif A.; Michel, Carine
  • ACS Catalysis, Vol. 6, Issue 12
  • DOI: 10.1021/acscatal.6b02253

Transition-State Enthalpy and Entropy Effects on Reactivity and Selectivity in Hydrogenolysis of n -Alkanes
journal, November 2013

  • Flaherty, David W.; Iglesia, Enrique
  • Journal of the American Chemical Society, Vol. 135, Issue 49
  • DOI: 10.1021/ja4093743

Adsorbate Entropies with Complete Potential Energy Sampling in Microkinetic Modeling
journal, March 2017

  • Jørgensen, Mikkel; Grönbeck, Henrik
  • The Journal of Physical Chemistry C, Vol. 121, Issue 13
  • DOI: 10.1021/acs.jpcc.6b11487

Benchmark First-Principles Calculations of Adsorbate Free Energies
journal, January 2018

Calculation of Free Energy Profiles for Elementary Bimolecular Reactions by ab Initio Molecular Dynamics:  Sampling Methods and Thermostat Considerations
journal, March 2004

  • Kelly, Evan; Seth, Michael; Ziegler, Tom
  • The Journal of Physical Chemistry A, Vol. 108, Issue 12
  • DOI: 10.1021/jp036007v

Ab initio calculations of free-energy reaction barriers
journal, January 2008

Interaction of Amino Acids with the Au(111) Surface: Adsorption Free Energies from Molecular Dynamics Simulations
journal, June 2010

  • Hoefling, Martin; Iori, Francesco; Corni, Stefano
  • Langmuir, Vol. 26, Issue 11
  • DOI: 10.1021/la904765u

Free Energy of Adsorption of Water and Metal Ions on the {101̄4} Calcite Surface
journal, August 2004

  • Kerisit, Sebastien; Parker, Stephen C.
  • Journal of the American Chemical Society, Vol. 126, Issue 32
  • DOI: 10.1021/ja0487776

Adsorption of a Sodium Ion on a Smectite Clay from Constrained Ab Initio Molecular Dynamics Simulations
journal, November 2008

  • Suter, J. L.; Boek, E. S.; Sprik, M.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 48
  • DOI: 10.1021/jp075946a

Molecular Dynamics Simulations of Adsorption of Amino Acid Side Chain Analogues and a Titanium Binding Peptide on the TiO 2 (100) Surface
journal, August 2015

  • Brandt, Erik G.; Lyubartsev, Alexander P.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 32
  • DOI: 10.1021/acs.jpcc.5b02670

Adsorption Free Energy of Single Amino Acids at the Rutile (110)/Water Interface Studied by Well-Tempered Metadynamics
journal, May 2018

  • YazdanYar, Azade; Aschauer, Ulrich; Bowen, Paul
  • The Journal of Physical Chemistry C, Vol. 122, Issue 21
  • DOI: 10.1021/acs.jpcc.7b12614

Current Status of Transition-State Theory
journal, January 1996

  • Truhlar, Donald G.; Garrett, Bruce C.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry, Vol. 100, Issue 31
  • DOI: 10.1021/jp953748q

Estimating entropies from molecular dynamics simulations
journal, February 2004

  • Peter, Christine; Oostenbrink, Chris; van Dorp, Arthur
  • The Journal of Chemical Physics, Vol. 120, Issue 6
  • DOI: 10.1063/1.1636153

Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations
journal, June 2010

  • Lin, Shiang-Tai; Maiti, Prabal K.; Goddard, William A.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 24
  • DOI: 10.1021/jp103120q

Application of Transition-State Theory to Gas-Surface Reactions: Barrierless Adsorption on Clean Surfaces
journal, December 1994

  • Pitt, Ian G.; Gilbert, Robert G.; Ryan, Keith R.
  • The Journal of Physical Chemistry, Vol. 98, Issue 49
  • DOI: 10.1021/j100100a031

Kinetic Prefactors of Reactions on Solid Surfaces
journal, January 2013

  • Campbell, Charles T.; Árnadóttir, Líney; Sellers, Jason R. V.
  • Zeitschrift für Physikalische Chemie, Vol. 227, Issue 9-11
  • DOI: 10.1524/zpch.2013.0395

Equilibrium Constants and Rate Constants for Adsorbates: Two-Dimensional (2D) Ideal Gas, 2D Ideal Lattice Gas, and Ideal Hindered Translator Models
journal, May 2016

  • Campbell, Charles T.; Sprowl, Lynza H.; Árnadóttir, Líney
  • The Journal of Physical Chemistry C, Vol. 120, Issue 19
  • DOI: 10.1021/acs.jpcc.6b00975

Quantum Chemical Free Energies: Structure Optimization and Vibrational Frequencies in Normal Modes
journal, October 2013

  • Piccini, GiovanniMaria; Sauer, Joachim
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 11
  • DOI: 10.1021/ct4005504

Effect of Anharmonicity on Adsorption Thermodynamics
journal, May 2014

  • Piccini, GiovanniMaria; Sauer, Joachim
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 6
  • DOI: 10.1021/ct500291x

Supramolecular Binding Thermodynamics by Dispersion-Corrected Density Functional Theory
journal, July 2012

Modeling the HCOOH/CO 2 Electrocatalytic Reaction: When Details Are Key
journal, June 2015

  • Steinmann, Stephan N.; Michel, Carine; Schwiedernoch, Renate
  • ChemPhysChem, Vol. 16, Issue 11
  • DOI: 10.1002/cphc.201500187

Effect of temperature and branching on the nature and stability of alkene cracking intermediates in H-ZSM-5
journal, January 2017

Proton exchange of small hydrocarbons over acidic chabazite: Ab initio study of entropic effects
journal, August 2007

Zeolite Adsorption Free Energies from ab Initio Potentials of Mean Force
journal, January 2018

  • Li, Hui; Paolucci, Christopher; Schneider, William F.
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 2
  • DOI: 10.1021/acs.jctc.7b00716

Absolute and Relative Entropies from Computer Simulation with Applications to Ligand Binding
journal, April 2005

  • Carlsson, Jens; Åqvist, Johan
  • The Journal of Physical Chemistry B, Vol. 109, Issue 13
  • DOI: 10.1021/jp046022f

Calculation of Reaction Free Energies in Solution: A Comparison of Current Approaches
journal, January 2018

  • Besora, Maria; Vidossich, Pietro; Lledós, Agustí
  • The Journal of Physical Chemistry A, Vol. 122, Issue 5
  • DOI: 10.1021/acs.jpca.7b11580

Theory of Free Energy and Entropy in Noncovalent Binding
journal, September 2009

  • Zhou, Huan-Xiang; Gilson, Michael K.
  • Chemical Reviews, Vol. 109, Issue 9
  • DOI: 10.1021/cr800551w

Ab initiomolecular dynamics for liquid metals
journal, January 1993

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

Projector augmented-wave method
journal, December 1994

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

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

Real-Time Observation of Surface Bond Breaking with an X-ray Laser
journal, March 2013

Computational characterization and modeling of buckyball tweezers: density functional study of concave–convex π⋯π interactions
journal, January 2008

  • Zhao, Yan; Truhlar, Donald G.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 19
  • DOI: 10.1039/b717744e

Vibrational spectrum of brucite, Mg(OH)2: a periodic ab initio quantum mechanical calculation including OH anharmonicity
journal, October 2004

Molecular dynamics simulations at constant pressure and/or temperature
journal, February 1980

  • Andersen, Hans C.
  • The Journal of Chemical Physics, Vol. 72, Issue 4
  • DOI: 10.1063/1.439486

Advantages of a Lowe-Andersen thermostat in molecular dynamics simulations
journal, May 2006

  • Koopman, E. A.; Lowe, C. P.
  • The Journal of Chemical Physics, Vol. 124, Issue 20
  • DOI: 10.1063/1.2198824

Canonical sampling through velocity rescaling
journal, January 2007

  • Bussi, Giovanni; Donadio, Davide; Parrinello, Michele
  • The Journal of Chemical Physics, Vol. 126, Issue 1
  • DOI: 10.1063/1.2408420

Geometry optimization of periodic systems using internal coordinates
journal, March 2005

  • Bučko, Tomáš; Hafner, Jürgen; Ángyán, János G.
  • The Journal of Chemical Physics, Vol. 122, Issue 12
  • DOI: 10.1063/1.1864932

Tracing the minimum-energy path on the free-energy surface
journal, August 2005

  • Fleurat-Lessard, Paul; Ziegler, Tom
  • The Journal of Chemical Physics, Vol. 123, Issue 8
  • DOI: 10.1063/1.1948367

Error estimates on averages of correlated data
journal, July 1989

  • Flyvbjerg, H.; Petersen, H. G.
  • The Journal of Chemical Physics, Vol. 91, Issue 1
  • DOI: 10.1063/1.457480

Prospects of CO2 Utilization via Direct Heterogeneous Electrochemical Reduction
journal, December 2010

  • Whipple, Devin T.; Kenis, Paul J. A.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 24, p. 3451-3458
  • DOI: 10.1021/jz1012627

Precursor-mediated adsorption and desorption: a theoretical analysis
journal, March 1988

Rational design of heterogeneous catalysts for biomass conversion – Inputs from computational chemistry
journal, April 2018

Tuning the Adsorption of Aromatic Molecules on Platinum via Halogenation
journal, March 2014

  • Peköz, Rengin; Johnston, Karen; Donadio, Davide
  • The Journal of Physical Chemistry C, Vol. 118, Issue 12
  • DOI: 10.1021/jp411422x

Thermally assisted tunneling: CH 4 dissociation on Pt(111)
journal, July 1991

Surface Temperature Dependence of Methane Activation on Ni(111)
journal, November 2009

  • Killelea, D. R.; Campbell, V. L.; Shuman, N. S.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 48
  • DOI: 10.1021/jp9065339

Cutting a chemical bond with demon's scissors: Mode- and bond-selective reactivity of methane on metal surfaces
journal, October 2015

Catalytic Hydrogenation of Unsaturated Aldehydes on Pt(111): Understanding the Selectivity from First-Principles Calculations
journal, August 2005

  • Loffreda, David; Delbecq, Françoise; Vigné, Fabienne
  • Angewandte Chemie International Edition, Vol. 44, Issue 33
  • DOI: 10.1002/anie.200500913

The statistical-thermodynamic basis for computation of binding affinities: a critical review
journal, March 1997

Quantum Chemical Free Energies: Structure Optimization and Vibrational Frequencies in Normal Modes
journal, October 2013

  • Piccini, GiovanniMaria; Sauer, Joachim
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 11
  • DOI: 10.1021/ct4005504

Free Energy of Adsorption of Water and Metal Ions on the {101̄4} Calcite Surface
journal, August 2004

  • Kerisit, Sebastien; Parker, Stephen C.
  • Journal of the American Chemical Society, Vol. 126, Issue 32
  • DOI: 10.1021/ja0487776

Absolute and Relative Entropies from Computer Simulation with Applications to Ligand Binding
journal, April 2005

  • Carlsson, Jens; Åqvist, Johan
  • The Journal of Physical Chemistry B, Vol. 109, Issue 13
  • DOI: 10.1021/jp046022f

Tuning the Adsorption of Aromatic Molecules on Platinum via Halogenation
journal, March 2014

  • Peköz, Rengin; Johnston, Karen; Donadio, Davide
  • The Journal of Physical Chemistry C, Vol. 118, Issue 12
  • DOI: 10.1021/jp411422x

Current Status of Transition-State Theory
journal, January 1996

  • Truhlar, Donald G.; Garrett, Bruce C.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry, Vol. 100, Issue 31
  • DOI: 10.1021/jp953748q

Interaction of Amino Acids with the Au(111) Surface: Adsorption Free Energies from Molecular Dynamics Simulations
journal, June 2010

  • Hoefling, Martin; Iori, Francesco; Corni, Stefano
  • Langmuir, Vol. 26, Issue 11
  • DOI: 10.1021/la904765u

Geometry optimization of periodic systems using internal coordinates
journal, March 2005

  • Bučko, Tomáš; Hafner, Jürgen; Ángyán, János G.
  • The Journal of Chemical Physics, Vol. 122, Issue 12
  • DOI: 10.1063/1.1864932

Tracing the minimum-energy path on the free-energy surface
journal, August 2005

  • Fleurat-Lessard, Paul; Ziegler, Tom
  • The Journal of Chemical Physics, Vol. 123, Issue 8
  • DOI: 10.1063/1.1948367

Error estimates on averages of correlated data
journal, July 1989

  • Flyvbjerg, H.; Petersen, H. G.
  • The Journal of Chemical Physics, Vol. 91, Issue 1
  • DOI: 10.1063/1.457480

Ab initio calculations of free-energy reaction barriers
journal, January 2008

Real-Time Observation of Surface Bond Breaking with an X-ray Laser
journal, March 2013

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: