ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

Simulation of Adsorption Processes at Metallic Interfaces: An Image Charge Augmented QM/MM Approach

View Author Information
Institute of Physical Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland
The Abdus Salam International Centre for Theoretical Physics, Strada Costiera 11, I-34151 Trieste, Italy
§ Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, Überlandstrasse 129, CH-8600 Dübendorf, Switzerland
Cite this: J. Chem. Theory Comput. 2013, 9, 11, 5086–5097
Publication Date (Web):September 24, 2013
Copyright © 2013 American Chemical Society

    Article Views





    Other access options
    Supporting Info (1)»


    Abstract Image

    A novel method for including polarization effects within hybrid quantum mechanics/molecular mechanics (QM/MM) simulations of adsorbate-metal systems is presented. The interactions between adsorbate (QM) and metallic substrate (MM) are described at the MM level of theory. Induction effects are additionally accounted for by applying the image charge formulation. The charge distribution induced within the metallic substrate is modeled by a set of Gaussian charges (image charges) centered at the metal atoms. The image charges and the electrostatic response of the QM potential are determined self-consistently by imposing the constant-potential condition within the metal. The implementation is embedded in a highly efficient Gaussian and plane wave framework and is naturally suited for periodic systems. Even though the electronic properties of the metallic substrate are not taken into account explicitly, the augmented QM/MM scheme can reproduce characteristic polarization effects of the adsorbate. The method is assessed through the investigation of structural and electronic properties of benzene, nitrobenzene, thymine, and guanine on Au(111). The study of small water clusters adsorbed on Pt(111) is also reported in order to demonstrate that the approach provides a sizable correction of the MM-based interactions between adsorbate and substrate. Large-scale molecular dynamics (MD) simulations of a water film in contact with a Pt(111) surface show that the method is suitable for simulations of liquid/metal interfaces at reduced computational cost.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    Jump To

    Contour plot of the electrostatic potential for nitrobenzene on Au(111), charges induced in finite Au(111) slabs by Cl and Na+, Δρelec for benzene on Au(111) as obtained by full DFT, variation of the dipole moment (x-, y-, and z-component) for guanine on Au(111), plane-averaged electrostatic potential of 151 H2O on Pt(111) for a particular snapshot of the MD simulation. This material is available free of charge via the Internet at

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 62 publications.

    1. John H. Hymel, Shahriar N. Khan, John P. Pederson, Jesse G. McDaniel. Computational Electrosynthesis Study of Anodic Intramolecular Olefin Coupling: Elucidating the Role of the Electrical Double Layer. The Journal of Physical Chemistry C 2023, 127 (39) , 19489-19508.
    2. Denys Biriukov, Zdenek Futera. Adsorption of Amino Acids at the Gold/Aqueous Interface: Effect of an External Electric Field. The Journal of Physical Chemistry C 2021, 125 (14) , 7856-7867.
    3. Qiang Cui, Tanmoy Pal, Luke Xie. Biomolecular QM/MM Simulations: What Are Some of the “Burning Issues”?. The Journal of Physical Chemistry B 2021, 125 (3) , 689-702.
    4. Dmitry Bedrov, Jean-Philip Piquemal, Oleg Borodin, Alexander D. MacKerell, Jr., Benoît Roux, Christian Schröder. Molecular Dynamics Simulations of Ionic Liquids and Electrolytes Using Polarizable Force Fields. Chemical Reviews 2019, 119 (13) , 7940-7995.
    5. Muhammad Saleh, Thomas S. Hofer. A DFTB/MM MD Approach for Solid-State Interfaces: Structural and Dynamical Properties of H2O and NH3 on R-TiO2 (001). The Journal of Physical Chemistry C 2019, 123 (12) , 7230-7245.
    6. Zdenek Futera, Jochen Blumberger. Adsorption of Amino Acids on Gold: Assessing the Accuracy of the GolP-CHARMM Force Field and Parametrization of Au–S Bonds. Journal of Chemical Theory and Computation 2019, 15 (1) , 613-624.
    7. Stephan N. Steinmann, Rodrigo Ferreira De Morais, Andreas W. Götz, Paul Fleurat-Lessard, Marcella Iannuzzi, Philippe Sautet, Carine Michel. Force Field for Water over Pt(111): Development, Assessment, and Comparison. Journal of Chemical Theory and Computation 2018, 14 (6) , 3238-3251.
    8. A. O. Dohn, E. Ö. Jónsson, G. Levi, J. J. Mortensen, O. Lopez-Acevedo, K. S. Thygesen, K. W. Jacobsen, J. Ulstrup, N. E. Henriksen, K. B. Møller, and H. Jónsson . Grid-Based Projector Augmented Wave (GPAW) Implementation of Quantum Mechanics/Molecular Mechanics (QM/MM) Electrostatic Embedding and Application to a Solvated Diplatinum Complex. Journal of Chemical Theory and Computation 2017, 13 (12) , 6010-6022.
    9. Geun Ho Gu, Benjamin Schweitzer, Carine Michel, Stephan N. Steinmann, Philippe Sautet, and Dionisios G. Vlachos . Group Additivity for Aqueous Phase Thermochemical Properties of Alcohols on Pt(111). The Journal of Physical Chemistry C 2017, 121 (39) , 21510-21519.
    10. Jasmin Kaur and Rama Kant . Theory of Work Function and Potential of Zero Charge for Metal Nanostructured and Rough Electrodes. The Journal of Physical Chemistry C 2017, 121 (24) , 13059-13069.
    11. Xavier Bouju, Cristina Mattioli, Grégory Franc, Adeline Pujol, and André Gourdon . Bicomponent Supramolecular Architectures at the Vacuum–Solid Interface. Chemical Reviews 2017, 117 (3) , 1407-1444.
    12. Guglielmo Fernandez Garcia, Alessandro Lunghi, Federico Totti, and Roberta Sessoli . Toward Mesoscale Properties of Self-Assembled Monolayers of SMM on Au(111): An Integrated Ad Hoc FF and DFT Study. The Journal of Physical Chemistry C 2016, 120 (27) , 14774-14781.
    13. Olle Björneholm, Martin H. Hansen, Andrew Hodgson, Li-Min Liu, David T. Limmer, Angelos Michaelides, Philipp Pedevilla, Jan Rossmeisl, Huaze Shen, Gabriele Tocci, Eric Tyrode, Marie-Madeleine Walz, Josephina Werner, and Hendrik Bluhm . Water at Interfaces. Chemical Reviews 2016, 116 (13) , 7698-7726.
    14. Xin Li, Vincenzo Carravetta, Cui Li, Susanna Monti, Zilvinas Rinkevicius, and Hans Ågren . Optical Properties of Gold Nanoclusters Functionalized with a Small Organic Compound: Modeling by an Integrated Quantum-Classical Approach. Journal of Chemical Theory and Computation 2016, 12 (7) , 3325-3339.
    15. Zilvinas Rinkevicius, Jaime A. R. Sandberg, Xin Li, Mathieu Linares, Patrick Norman, and Hans Ågren . Hybrid Complex Polarization Propagator/Molecular Mechanics Method for Heterogeneous Environments. Journal of Chemical Theory and Computation 2016, 12 (6) , 2661-2667.
    16. Benjamin Rotenberg and Mathieu Salanne . Structural Transitions at Ionic Liquid Interfaces. The Journal of Physical Chemistry Letters 2015, 6 (24) , 4978-4985.
    17. Thomas S. Hofer and Andreas O. Tirler . Combining 2d-Periodic Quantum Chemistry with Molecular Force Fields: A Novel QM/MM Procedure for the Treatment of Solid-State Surfaces and Interfaces. Journal of Chemical Theory and Computation 2015, 11 (12) , 5873-5887.
    18. Jenel Vatamanu and Dmitry Bedrov . Capacitive Energy Storage: Current and Future Challenges. The Journal of Physical Chemistry Letters 2015, 6 (18) , 3594-3609.
    19. Jenel Vatamanu, Mihaela Vatamanu, and Dmitry Bedrov . Non-Faradaic Energy Storage by Room Temperature Ionic Liquids in Nanoporous Electrodes. ACS Nano 2015, 9 (6) , 5999-6017.
    20. Xin Li, Zilvinas Rinkevicius, and Hans Ågren . Two-Photon Absorption of Metal-Assisted Chromophores. Journal of Chemical Theory and Computation 2014, 10 (12) , 5630-5639.
    21. Puja Goyal, Hu-Jun Qian, Stephan Irle, Xiya Lu, Daniel Roston, Toshifumi Mori, Marcus Elstner, and Qiang Cui . Molecular Simulation of Water and Hydration Effects in Different Environments: Challenges and Developments for DFTB Based Models. The Journal of Physical Chemistry B 2014, 118 (38) , 11007-11027.
    22. Xin Li, Zilvinas Rinkevicius, and Hans Ågren . Electronic Circular Dichroism of Surface-Adsorbed Molecules by Means of Quantum Mechanics Capacitance Molecular Mechanics. The Journal of Physical Chemistry C 2014, 118 (11) , 5833-5840.
    23. Zilvinas Rinkevicius, Xin Li, Jaime A. R. Sandberg, Kurt V. Mikkelsen, and Hans Ågren . A Hybrid Density Functional Theory/Molecular Mechanics Approach for Linear Response Properties in Heterogeneous Environments. Journal of Chemical Theory and Computation 2014, 10 (3) , 989-1003.
    24. Phillip Seeber, Sebastian Seidenath, Johannes Steinmetzer, Stefanie Gräfe. Growing Spicy ONIOMs : Extending and generalizing concepts of ONIOM and many body expansions. WIREs Computational Molecular Science 2023, 13 (3)
    25. Maria Fyta. Functionalized electrodes embedded in nanopores: read‐out enhancement?. Chemistry – An Asian Journal 2023, 18 (1)
    26. Márcio S. Gomes-Filho, Aline O. Pereira, Gustavo T Feliciano, Luana S. Pedroza, Mauricio D. Coutinho-Neto. Extending the applicability of popular force fields for describing water/metal interfaces: application to water/Pd(111). Physica Scripta 2023, 98 (1) , 015009.
    27. Matteo Briganti, Federico Totti. Molecular Magnets on Surfaces: In Silico Recipes for a Successful Marriage. 2023, 395-444.
    28. Ken Takahashi, Hiroshi Nakano, Hirofumi Sato. Accelerated constant-voltage quantum mechanical/molecular mechanical method for molecular systems at electrochemical interfaces. The Journal of Chemical Physics 2022, 157 (23)
    29. Peng Li, Yuwen Liu, Shengli Chen. Microscopic EDL structures and charge–potential relation on stepped platinum surface: Insights from the ab initio molecular dynamics simulations. The Journal of Chemical Physics 2022, 156 (10)
    30. Jenel Vatamanu, Lidan Xing, Dmitry Bedrov. Modeling Methods of Ionic Liquids at Charged Electrode Surfaces. 2022, 901-910.
    31. Xiao‐Hui Yang, Yong‐Bin Zhuang, Jia‐Xin Zhu, Jia‐Bo Le, Jun Cheng. Recent progress on multiscale modeling of electrochemistry. WIREs Computational Molecular Science 2022, 12 (1)
    32. Chenlu Wang, Yanlei Wang, Zhongdong Gan, Yumiao Lu, Cheng Qian, Feng Huo, Hongyan He, Suojiang Zhang. Topological engineering of two-dimensional ionic liquid islands for high structural stability and CO 2 adsorption selectivity. Chemical Science 2021, 12 (47) , 15503-15510.
    33. Jia‐Bo Le, Xiao‐Hui Yang, Yong‐Bing Zhuang, Feng Wang, Jun Cheng. Ab initio modeling of electrochemical interfaces and determination of electrode potentials. 2021, 173-200.
    34. Jenel Vatamanu, Lidan Xing, Dmitry Bedrov. Modeling Methods of Ionic Liquids at Charged Electrode Surfaces. 2021, 1-9.
    35. L. El Atouani, K. Sbiaai, A. Hasnaoui. Insights into NinTim clusters adsorption and diffusion on B2-NiTi phase from atomistic simulations. Surface Science 2020, 701 , 121655.
    36. Paul Clabaut, Ruben Staub, Joachim Galiana, Elise Antonetti, Stephan N. Steinmann. Water adlayers on noble metal surfaces: Insights from energy decomposition analysis. The Journal of Chemical Physics 2020, 153 (5)
    37. Ken Takahashi, Hiroshi Nakano, Hirofumi Sato. A polarizable molecular dynamics method for electrode–electrolyte interfacial electron transfer under the constant chemical-potential-difference condition on the electrode electrons. The Journal of Chemical Physics 2020, 153 (5)
    38. Gabriele Tocci, Maria Bilichenko, Laurent Joly, Marcella Iannuzzi. Ab initio nanofluidics: disentangling the role of the energy landscape and of density correlations on liquid/solid friction. Nanoscale 2020, 12 (20) , 10994-11000.
    39. Thomas D. Kühne, Marcella Iannuzzi, Mauro Del Ben, Vladimir V. Rybkin, Patrick Seewald, Frederick Stein, Teodoro Laino, Rustam Z. Khaliullin, Ole Schütt, Florian Schiffmann, Dorothea Golze, Jan Wilhelm, Sergey Chulkov, Mohammad Hossein Bani-Hashemian, Valéry Weber, Urban Borštnik, Mathieu Taillefumier, Alice Shoshana Jakobovits, Alfio Lazzaro, Hans Pabst, Tiziano Müller, Robert Schade, Manuel Guidon, Samuel Andermatt, Nico Holmberg, Gregory K. Schenter, Anna Hehn, Augustin Bussy, Fabian Belleflamme, Gloria Tabacchi, Andreas Glöß, Michael Lass, Iain Bethune, Christopher J. Mundy, Christian Plessl, Matt Watkins, Joost VandeVondele, Matthias Krack, Jürg Hutter. CP2K: An electronic structure and molecular dynamics software package - Quickstep: Efficient and accurate electronic structure calculations. The Journal of Chemical Physics 2020, 152 (19)
    40. Kathleen Schwarz, Ravishankar Sundararaman. The electrochemical interface in first-principles calculations. Surface Science Reports 2020, 75 (2) , 100492.
    41. Laura Katharina Scarbath-Evers, René Hammer, Dorothea Golze, Martin Brehm, Daniel Sebastiani, Wolf Widdra. From flat to tilted: gradual interfaces in organic thin film growth. Nanoscale 2020, 12 (6) , 3834-3845.
    42. Thomas Dufils, Guillaume Jeanmairet, Benjamin Rotenberg, Michiel Sprik, Mathieu Salanne. Simulating Electrochemical Systems by Combining the Finite Field Method with a Constant Potential Electrode. Physical Review Letters 2019, 123 (19)
    43. Maofeng Dou, Frank C. Maier, Maria Fyta. The influence of a solvent on the electronic transport across diamondoid-functionalized biosensing electrodes. Nanoscale 2019, 11 (30) , 14216-14225.
    44. Niko Prasetyo, Thomas S. Hofer. Adsorption and dissociation of water molecules at the α-Al2O3(0001) surface: A 2-dimensional hybrid self-consistent charge density functional based tight-binding/molecular mechanics molecular dynamics (2D SCC-DFTB/MM MD) simulation study. Computational Materials Science 2019, 164 , 195-204.
    45. Frank C. Maier, Chandra S. Sarap, Maofeng Dou, Ganesh Sivaraman, Maria Fyta. Diamondoid-functionalized nanogaps: from small molecules to electronic biosensing. The European Physical Journal Special Topics 2019, 227 (14) , 1681-1692.
    46. Isidro Lorenzo Geada, Hadi Ramezani-Dakhel, Tariq Jamil, Marialore Sulpizi, Hendrik Heinz. Insight into induced charges at metal surfaces and biointerfaces using a polarizable Lennard–Jones potential. Nature Communications 2018, 9 (1)
    47. Xiuli Xia, Yuanzhi Shao. Quantum mechanical studies of full‐shell noble metal nanoclusters in water. International Journal of Quantum Chemistry 2018, 118 (20)
    48. Thomas S. Hofer, Sam P. de Visser. Editorial: Quantum Mechanical/Molecular Mechanical Approaches for the Investigation of Chemical Systems – Recent Developments and Advanced Applications. Frontiers in Chemistry 2018, 6
    49. Xiuli Xia, Yuanzhi Shao. Ab initio study on the structural and electronic properties of water surrounding a multifunctional nanoprobe. Physica B: Condensed Matter 2018, 530 , 69-74.
    50. Jonas Feldt, Sebastião Miranda, Frederico Pratas, Nuno Roma, Pedro Tomás, Ricardo A. Mata. Optimization and benchmarking of a perturbative Metropolis Monte Carlo quantum mechanics/molecular mechanics program. The Journal of Chemical Physics 2017, 147 (24)
    51. Jenel Vatamanu, Dmitry Bedrov, Oleg Borodin. On the application of constant electrode potential simulation techniques in atomistic modelling of electric double layers. Molecular Simulation 2017, 43 (10-11) , 838-849.
    52. Jiabo Le, Marcella Iannuzzi, Angel Cuesta, Jun Cheng. Determining Potentials of Zero Charge of Metal Electrodes versus the Standard Hydrogen Electrode from Density-Functional-Theory-Based Molecular Dynamics. Physical Review Letters 2017, 119 (1)
    53. Tatsuya Shinagawa, Zhen Cao, Luigi Cavallo, Kazuhiro Takanabe. Photophysics and electrochemistry relevant to photocatalytic water splitting involved at solid–electrolyte interfaces. Journal of Energy Chemistry 2017, 26 (2) , 259-269.
    54. Mohammadreza Samieegohar, Heng Ma, Feng Sha, Md Symon Jahan Sajib, G. Iván Guerrero-García, Tao Wei. Understanding the interfacial behavior of lysozyme on Au (111) surfaces with multiscale simulations. Applied Physics Letters 2017, 110 (7)
    55. Dorothea Golze, Niels Benedikter, Marcella Iannuzzi, Jan Wilhelm, Jürg Hutter. Fast evaluation of solid harmonic Gaussian integrals for local resolution-of-the-identity methods and range-separated hybrid functionals. The Journal of Chemical Physics 2017, 146 (3)
    56. Jenel Vatamanu, Oleg Borodin, Marco Olguin, Gleb Yushin, Dmitry Bedrov. Charge storage at the nanoscale: understanding the trends from the molecular scale perspective. Journal of Materials Chemistry A 2017, 5 (40) , 21049-21076.
    57. Diego Hunt, Veronica M Sanchez, Damián A Scherlis. A quantum-mechanics molecular-mechanics scheme for extended systems. Journal of Physics: Condensed Matter 2016, 28 (33) , 335201.
    58. Hendrik Heinz, Hadi Ramezani-Dakhel. Simulations of inorganic–bioorganic interfaces to discover new materials: insights, comparisons to experiment, challenges, and opportunities. Chemical Society Reviews 2016, 45 (2) , 412-448.
    59. Suresh Kondati Natarajan, Jörg Behler. Neural network molecular dynamics simulations of solid–liquid interfaces: water at low-index copper surfaces. Physical Chemistry Chemical Physics 2016, 18 (41) , 28704-28725.
    60. Jenel Vatamanu, Xiaojuan Ni, Feng Liu, Dmitry Bedrov. Tailoring graphene-based electrodes from semiconducting to metallic to increase the energy density in supercapacitors. Nanotechnology 2015, 26 (46) , 464001.
    61. Dorothea Golze, Jürg Hutter, Marcella Iannuzzi. Wetting of water on hexagonal boron nitride@Rh(111): a QM/MM model based on atomic charges derived for nano-structured substrates. Physical Chemistry Chemical Physics 2015, 17 (22) , 14307-14316.
    62. David T. Limmer, Adam P. Willard. Nanoscale heterogeneity at the aqueous electrolyte–electrode interface. Chemical Physics Letters 2015, 620 , 144-150.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect