Benchmarking Semiempirical Methods To Compute Electrochemical Formal Potentials
Abstract
Computational methods to predict and tune electrochemical redox potentials are important for the development of energy technologies. Here, we benchmark several semiempirical models to compute reduction potentials of organic molecules, comparing approaches based on (1) energy differences between the S0 and one-electron-reduced D0 states of the isolated molecules and (2) an orbital energy shift approach based on tuning the charge-transfer triplet energy of the Ag20-molecule complex; the second model enables explicit modeling of electrode–molecule interactions. For molecules in solution, the two models yield nearly identical results. Both PM7 and PM6 predict formal potentials with only a slight loss of accuracy compared to standard density functional theory models, and the results are robust across several choices of geometries and implicit solvent models. PM6 and PM7 show dramatically improved accuracy over older semiempirical Hamiltonians (MNDO, AM1, PM3, and INDO/S). However, our recently developed INDO parameters model the electronic properties of our Ag20 model electrode much more accurately than does PM7. These results demonstrate the need for further development of semiempirical models to accurately model molecules on surfaces.
- Authors:
-
- Department of Chemistry, Northwestern University 2145 Sheridan Road, Evanston, Illinois 60208, United States
- Publication Date:
- Research Org.:
- Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1464278
- Alternate Identifier(s):
- OSTI ID: 1508603
- Grant/Contract Number:
- SC0004752
- Resource Type:
- Published Article
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Volume: 122 Journal Issue: 33; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 97 MATHEMATICS AND COMPUTING
Citation Formats
Gieseking, Rebecca L. M., Ratner, Mark A., and Schatz, George C. Benchmarking Semiempirical Methods To Compute Electrochemical Formal Potentials. United States: N. p., 2018.
Web. doi:10.1021/acs.jpca.8b05143.
Gieseking, Rebecca L. M., Ratner, Mark A., & Schatz, George C. Benchmarking Semiempirical Methods To Compute Electrochemical Formal Potentials. United States. https://doi.org/10.1021/acs.jpca.8b05143
Gieseking, Rebecca L. M., Ratner, Mark A., and Schatz, George C. Thu .
"Benchmarking Semiempirical Methods To Compute Electrochemical Formal Potentials". United States. https://doi.org/10.1021/acs.jpca.8b05143.
@article{osti_1464278,
title = {Benchmarking Semiempirical Methods To Compute Electrochemical Formal Potentials},
author = {Gieseking, Rebecca L. M. and Ratner, Mark A. and Schatz, George C.},
abstractNote = {Computational methods to predict and tune electrochemical redox potentials are important for the development of energy technologies. Here, we benchmark several semiempirical models to compute reduction potentials of organic molecules, comparing approaches based on (1) energy differences between the S0 and one-electron-reduced D0 states of the isolated molecules and (2) an orbital energy shift approach based on tuning the charge-transfer triplet energy of the Ag20-molecule complex; the second model enables explicit modeling of electrode–molecule interactions. For molecules in solution, the two models yield nearly identical results. Both PM7 and PM6 predict formal potentials with only a slight loss of accuracy compared to standard density functional theory models, and the results are robust across several choices of geometries and implicit solvent models. PM6 and PM7 show dramatically improved accuracy over older semiempirical Hamiltonians (MNDO, AM1, PM3, and INDO/S). However, our recently developed INDO parameters model the electronic properties of our Ag20 model electrode much more accurately than does PM7. These results demonstrate the need for further development of semiempirical models to accurately model molecules on surfaces.},
doi = {10.1021/acs.jpca.8b05143},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 33,
volume = 122,
place = {United States},
year = {2018},
month = {7}
}
https://doi.org/10.1021/acs.jpca.8b05143
Works referenced in this record:
Experimental and Computed Absolute Redox Potentials of Polycyclic Aromatic Hydrocarbons are Highly Linearly Correlated Over a Wide Range of Structures and Potentials
journal, November 2010
- Davis, Anthony P.; Fry, Albert J.
- The Journal of Physical Chemistry A, Vol. 114, Issue 46
Optimization of solute cavities and van der Waals parameters inab initio MST-SCRF calculations of neutral molecules
journal, April 1994
- Bachs, M.; Luque, F. J.; Orozco, Modesto
- Journal of Computational Chemistry, Vol. 15, Issue 4
Building and testing correlations for the estimation of one-electron reduction potentials of a diverse set of organic molecules: ESTIMATING ONE-ELECTRON REDUCTION POTENTIALS
journal, January 2015
- Méndez-Hernández, Dalvin D.; Gillmore, Jason G.; Montano, Luis A.
- Journal of Physical Organic Chemistry, Vol. 28, Issue 5
Computational high-throughput screening of electrocatalytic materials for hydrogen evolution
journal, October 2006
- Greeley, Jeff; Jaramillo, Thomas F.; Bonde, Jacob
- Nature Materials, Vol. 5, Issue 11, p. 909-913
Modeling of electron transfer across electrochemical interfaces: State-of-the art and challenges for quantum and computational chemistry
journal, November 2015
- Nazmutdinov, Renat R.; Bronshtein, Michael D.; Zinkicheva, Tamara T.
- International Journal of Quantum Chemistry, Vol. 116, Issue 3
Modeling CO2 reduction on Pt(111)
journal, January 2013
- Shi, Chuan; O'Grady, Christopher P.; Peterson, Andrew A.
- Physical Chemistry Chemical Physics, Vol. 15, Issue 19
Advances in understanding mechanisms underpinning lithium–air batteries
journal, September 2016
- Aurbach, Doron; McCloskey, Bryan D.; Nazar, Linda F.
- Nature Energy, Vol. 1, Issue 9
Theoretical modeling of voltage effects and the chemical mechanism in surface-enhanced Raman scattering
journal, January 2017
- Gieseking, Rebecca L.; Ratner, Mark A.; Schatz, George C.
- Faraday Discussions, Vol. 205
Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges
journal, February 2017
- Canepa, Pieremanuele; Sai Gautam, Gopalakrishnan; Hannah, Daniel C.
- Chemical Reviews, Vol. 117, Issue 5
Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988
- Becke, A. D.
- Physical Review A, Vol. 38, Issue 6
Comparison of 6-31G*-based MST/SCRF and FEP evaluations of the free energies of hydration for small neutral molecules
journal, December 1993
- Orozco, Modesto; Jorgensen, William L.; Luque, F. J.
- Journal of Computational Chemistry, Vol. 14, Issue 12
Theory for C—N− and Ag—C vibrational frequency dependence on potential: cyanide on a silver electrode
journal, August 1981
- Anderson, Alfred B.; Kötz, Rüdiger; Yeager, Ernest
- Chemical Physics Letters, Vol. 82, Issue 1
How Potentials of Zero Charge and Potentials for Water Oxidation to OH(ads) on Pt(111) Electrodes Vary With Coverage
journal, September 2009
- Tian, Feng; Jinnouchi, Ryosuke; Anderson, Alfred B.
- The Journal of Physical Chemistry C, Vol. 113, Issue 40
van der Waals Volumes and Radii
journal, March 1964
- Bondi, A.
- The Journal of Physical Chemistry, Vol. 68, Issue 3, p. 441-451
Implementation of INDO/SCI with COSMO Implicit Solvation and Benchmarking for Solvatochromic Shifts
journal, December 2016
- Gieseking, Rebecca L.; Ratner, Mark A.; Schatz, George C.
- The Journal of Physical Chemistry A, Vol. 120, Issue 49
Modeling the electrified solid–liquid interface
journal, November 2008
- Rossmeisl, Jan; Skúlason, Egill; Björketun, Mårten E.
- Chemical Physics Letters, Vol. 466, Issue 1-3
A first-principles study of molecular oxygen dissociation at an electrode surface: a comparison of potential variation and coadsorption effects
journal, January 2008
- Wasileski, Sally A.; Janik, Michael J.
- Physical Chemistry Chemical Physics, Vol. 10, Issue 25
Chemistry with ADF
journal, January 2001
- te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
- Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
journal, January 1993
- Klamt, A.; Schüürmann, G.
- J. Chem. Soc., Perkin Trans. 2, Issue 5
From Discrete Electronic States to Plasmons: TDDFT Optical Absorption Properties of Ag n ( n = 10, 20, 35, 56, 84, 120) Tetrahedral Clusters
journal, July 2008
- Aikens, Christine M.; Li, Shuzhou; Schatz, George C.
- The Journal of Physical Chemistry C, Vol. 112, Issue 30
Electrochemical Hydrogen Oxidation on Pt(110): A Combined Direct Molecular Dynamics/Density Functional Theory Study
journal, March 2010
- Santana, Juan A.; Mateo, Juan J.; Ishikawa, Yasuyuki
- The Journal of Physical Chemistry C, Vol. 114, Issue 11
One-Electron and Two-Electron Transfers in Electrochemistry and Homogeneous Solution Reactions
journal, July 2008
- Evans, Dennis H.
- Chemical Reviews, Vol. 108, Issue 7
Expanding and Testing a Computational Method for Predicting the Ground State Reduction Potentials of Organic Molecules on the Basis of Empirical Correlation to Experiment
journal, July 2012
- Lynch, Eugene J.; Speelman, Amy L.; Curry, Bryce A.
- The Journal of Organic Chemistry, Vol. 77, Issue 15
Energy and fuels from electrochemical interfaces
journal, December 2016
- Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P.
- Nature Materials, Vol. 16, Issue 1
Semiempirical modeling of electrochemical charge transfer
journal, January 2017
- Gieseking, Rebecca L.; Ratner, Mark A.; Schatz, George C.
- Faraday Discussions, Vol. 199
Mechanistic Pathway in the Electrochemical Reduction of CO 2 on RuO 2
journal, June 2015
- Karamad, Mohammadreza; Hansen, Heine A.; Rossmeisl, Jan
- ACS Catalysis, Vol. 5, Issue 7
Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model
journal, June 1985
- Dewar, Michael J. S.; Zoebisch, Eve G.; Healy, Eamonn F.
- Journal of the American Chemical Society, Vol. 107, Issue 13
Heterogeneous catalytic conversion of CO 2 : a comprehensive theoretical review
journal, January 2015
- Li, Yawei; Chan, Siew Hwa; Sun, Qiang
- Nanoscale, Vol. 7, Issue 19
Calculation of One-Electron Redox Potentials Revisited. Is It Possible to Calculate Accurate Potentials with Density Functional Methods?
journal, June 2009
- Roy, Lindsay E.; Jakubikova, Elena; Guthrie, M. Graham
- The Journal of Physical Chemistry A, Vol. 113, Issue 24
Insights into Current Limitations of Density Functional Theory
journal, August 2008
- Cohen, A. J.; Mori-Sanchez, P.; Yang, W.
- Science, Vol. 321, Issue 5890
Electrochemical interface between an ionic liquid and a model metallic electrode
journal, February 2007
- Reed, Stewart K.; Lanning, Oliver J.; Madden, Paul A.
- The Journal of Chemical Physics, Vol. 126, Issue 8
Ab initio simulation of charged slabs at constant chemical potential
journal, July 2001
- Lozovoi, A. Y.; Alavi, A.; Kohanoff, J.
- The Journal of Chemical Physics, Vol. 115, Issue 4
An intermediate neglect of differential overlap model for second-row transition metal species
journal, January 1991
- Anderson, Wayne P.; Cundari, Thomas R.; Zerner, Michael C.
- International Journal of Quantum Chemistry, Vol. 39, Issue 1
Contemporary quantum chemical modelling of electrified interfaces
journal, July 1996
- Nazmutdinov, Renat R.; Shapnik, M. S.
- Electrochimica Acta, Vol. 41, Issue 14
A semiempirical model for the two-center repulsion integrals in the NDDO approximation
journal, January 1977
- Dewar, Michael J. S.; Thiel, Walter
- Theoretica Chimica Acta, Vol. 46, Issue 2
Design of rigid donor-acceptor systems with a low-lying charge-transfer state: an INDO model study of barrelene-based compounds
journal, November 1993
- Fox, Thomas; Kotzian, Manfred; Roesch, Notker
- The Journal of Physical Chemistry, Vol. 97, Issue 44
Time-Dependent Density Functional Theory Studies of Optical Properties of Ag Nanoparticles: Octahedra, Truncated Octahedra, and Icosahedra
journal, May 2012
- Bae, Gyun-Tack; Aikens, Christine M.
- The Journal of Physical Chemistry C, Vol. 116, Issue 18
The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage
journal, February 2015
- Kundu, Dipan; Talaie, Elahe; Duffort, Victor
- Angewandte Chemie International Edition, Vol. 54, Issue 11
Elucidation of the Electrochemical Activation of Water over Pd by First Principles
journal, January 2006
- Filhol, Jean-Sébastien; Neurock, Matthew
- Angewandte Chemie International Edition, Vol. 45, Issue 3
Optimization of parameters for semiempirical methods II. Applications
journal, March 1989
- Stewart, James J. P.
- Journal of Computational Chemistry, Vol. 10, Issue 2
Calculation of UV/Vis Spectra in Solution
journal, January 1996
- Klamt, Andreas
- The Journal of Physical Chemistry, Vol. 100, Issue 9
Optimization of parameters for semiempirical methods I. Method
journal, March 1989
- Stewart, James J. P.
- Journal of Computational Chemistry, Vol. 10, Issue 2
First-Principles Molecular Dynamics at a Constant Electrode Potential
journal, December 2012
- Bonnet, Nicéphore; Morishita, Tetsuya; Sugino, Osamu
- Physical Review Letters, Vol. 109, Issue 26
Ferrocene/Ferrocenium Redox Couple at Au(111)/Ionic Liquid and Au(111)/Acetonitrile Interfaces: A Molecular-Level View at the Elementary Act
journal, March 2014
- Nikitina, Victoria A.; Kislenko, Sergey A.; Nazmutdinov, Renat R.
- The Journal of Physical Chemistry C, Vol. 118, Issue 12
Optimization of parameters for semiempirical methods VI: more modifications to the NDDO approximations and re-optimization of parameters
journal, November 2012
- Stewart, James J. P.
- Journal of Molecular Modeling, Vol. 19, Issue 1
Widely available active sites on Ni 2 P for electrochemical hydrogen evolution – insights from first principles calculations
journal, January 2015
- Hansen, Martin H.; Stern, Lucas-Alexandre; Feng, Ligang
- Physical Chemistry Chemical Physics, Vol. 17, Issue 16
An intermediate neglect of differential overlap technique for spectroscopy of transition-metal complexes. Ferrocene
journal, January 1980
- Zerner, Michael C.; Loew, Gilda H.; Kirchner, Robert F.
- Journal of the American Chemical Society, Vol. 102, Issue 2
Are thermodynamic cycles necessary for continuum solvent calculation of pK a s and reduction potentials?
journal, January 2015
- Ho, Junming
- Physical Chemistry Chemical Physics, Vol. 17, Issue 4
Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena
journal, February 1995
- Klamt, Andreas
- The Journal of Physical Chemistry, Vol. 99, Issue 7
Computational electrochemistry: prediction of liquid-phase reduction potentials
journal, January 2014
- Marenich, Aleksandr V.; Ho, Junming; Coote, Michelle L.
- Phys. Chem. Chem. Phys., Vol. 16, Issue 29
DFT-INDO/S Modeling of New High Molar Extinction Coefficient Charge-Transfer Sensitizers for Solar Cell Applications
journal, January 2006
- Nazeeruddin, Mohammad K.; Wang, Qing; Cevey, Le
- Inorganic Chemistry, Vol. 45, Issue 2
Structures and reactions of hydronium, water, and hydroxyl on an iron electrode. Potential dependence
journal, February 1982
- Anderson, Alfred B.; Ray, N. K.
- The Journal of Physical Chemistry, Vol. 86, Issue 4
Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations
journal, October 2010
- Skúlason, Egill; Tripkovic, Vladimir; Björketun, Mårten E.
- The Journal of Physical Chemistry C, Vol. 114, Issue 42
Electric Field Effects in Electrochemical CO 2 Reduction
journal, September 2016
- Chen, Leanne D.; Urushihara, Makoto; Chan, Karen
- ACS Catalysis, Vol. 6, Issue 10
Density-functional approximation for the correlation energy of the inhomogeneous electron gas
journal, June 1986
- Perdew, John P.
- Physical Review B, Vol. 33, Issue 12
An overview of fuel cell technology: Fundamentals and applications
journal, April 2014
- Sharaf, Omar Z.; Orhan, Mehmet F.
- Renewable and Sustainable Energy Reviews, Vol. 32
Reduction of Systematic Uncertainty in DFT Redox Potentials of Transition-Metal Complexes
journal, March 2012
- Konezny, Steven J.; Doherty, Mark D.; Luca, Oana R.
- The Journal of Physical Chemistry C, Vol. 116, Issue 10
A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions
journal, January 2017
- Goerigk, Lars; Hansen, Andreas; Bauer, Christoph
- Physical Chemistry Chemical Physics, Vol. 19, Issue 48
The zero‐order regular approximation for relativistic effects: The effect of spin–orbit coupling in closed shell molecules
journal, October 1996
- van Lenthe, E.; Snijders, J. G.; Baerends, E. J.
- The Journal of Chemical Physics, Vol. 105, Issue 15
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
journal, January 2010
- Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix
- Energy & Environmental Science, Vol. 3, Issue 9
Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements
journal, September 2007
- Stewart, James J. P.
- Journal of Molecular Modeling, Vol. 13, Issue 12
Electrocatalytic oxygen evolution reaction for energy conversion and storage: A comprehensive review
journal, July 2017
- Tahir, Muhammad; Pan, Lun; Idrees, Faryal
- Nano Energy, Vol. 37
Efficient Computational Methods for Accurately Predicting Reduction Potentials of Organic Molecules
journal, June 2008
- Speelman, Amy L.; Gillmore, Jason G.
- The Journal of Physical Chemistry A, Vol. 112, Issue 25
Investigation of the Initial Steps of the Electrochemical Reduction of CO 2 on Pt Electrodes
journal, September 2014
- Dhar, Kalyan; Cavallotti, Carlo
- The Journal of Physical Chemistry A, Vol. 118, Issue 38
Ground states of molecules. 38. The MNDO method. Approximations and parameters
journal, June 1977
- Dewar, Michael J. S.; Thiel, Walter
- Journal of the American Chemical Society, Vol. 99, Issue 15
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004
- Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
- The Journal of Physical Chemistry B, Vol. 108, Issue 46
INDO/S parameters for gold
journal, January 2002
- Shapley, Warwick A.; Reimers, Jeffrey R.; Hush, Noel S.
- International Journal of Quantum Chemistry, Vol. 90, Issue 1
Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode
journal, January 2007
- Skúlason, Egill; Karlberg, Gustav S.; Rossmeisl, Jan
- Phys. Chem. Chem. Phys., Vol. 9, Issue 25
Combining theory and experiment in electrocatalysis: Insights into materials design
journal, January 2017
- Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F.
- Science, Vol. 355, Issue 6321
Semiempirical Modeling of Ag Nanoclusters: New Parameters for Optical Property Studies Enable Determination of Double Excitation Contributions to Plasmonic Excitation
journal, June 2016
- Gieseking, Rebecca L.; Ratner, Mark A.; Schatz, George C.
- The Journal of Physical Chemistry A, Vol. 120, Issue 26
MOPAC: A semiempirical molecular orbital program
journal, March 1990
- Stewart, James J. P.
- Journal of Computer-Aided Molecular Design, Vol. 4, Issue 1
Perspective on density functional theory
journal, April 2012
- Burke, Kieron
- The Journal of Chemical Physics, Vol. 136, Issue 15
Benchmark of Electronically Excited States for Semiempirical Methods: MNDO, AM1, PM3, OM1, OM2, OM3, INDO/S, and INDO/S2
journal, March 2010
- Silva-Junior, Mario R.; Thiel, Walter
- Journal of Chemical Theory and Computation, Vol. 6, Issue 5
First principles reaction modeling of the electrochemical interface: Consideration and calculation of a tunable surface potential from atomic and electronic structure
journal, April 2006
- Taylor, Christopher D.; Wasileski, Sally A.; Filhol, Jean-Sebastien
- Physical Review B, Vol. 73, Issue 16
Computed redox potentials and the design of bioreductive agents
journal, July 1988
- Reynolds, Christopher A.; King, Paul M.; Richards, W. Graham
- Nature, Vol. 334, Issue 6177