Redox Potentials and Acidity Constants from Density Functional Theory Based Molecular Dynamics
- Publication type:
- Journal article
- Metadata:
-
- Autoren
- Jun Cheng
- Xiandong Liu
- Joost VandeVondele
- Marialore Sulpizi
- Michiel Sprik
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000346683200012&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1021/ar500268y
- eISSN
- 1520-4898
- Externe Identifier
- Clarivate Analytics Document Solution ID: AX1BK
- PubMed Identifier: 25365148
- ISSN
- 0001-4842
- Ausgabe der Veröffentlichung
- 12
- Zeitschrift
- ACCOUNTS OF CHEMICAL RESEARCH
- Paginierung
- 3522 - 3529
- Datum der Veröffentlichung
- 2014
- Status
- Published
- Titel
- Redox Potentials and Acidity Constants from Density Functional Theory Based Molecular Dynamics
- Sub types
- Review
- Ausgabe der Zeitschrift
- 47
Data source: Web of Science (Lite)
- Other metadata sources:
-
- Autoren
- Jun Cheng
- Xiandong Liu
- Joost VandeVondele
- Marialore Sulpizi
- Michiel Sprik
- DOI
- 10.1021/ar500268y
- eISSN
- 1520-4898
- ISSN
- 0001-4842
- Ausgabe der Veröffentlichung
- 12
- Zeitschrift
- Accounts of Chemical Research
- Sprache
- en
- Online publication date
- 2014
- Paginierung
- 3522 - 3529
- Datum der Veröffentlichung
- 2014
- Status
- Published
- Herausgeber
- American Chemical Society (ACS)
- Herausgeber URL
- http://dx.doi.org/10.1021/ar500268y
- Datum der Datenerfassung
- 2023
- Titel
- Redox Potentials and Acidity Constants from Density Functional Theory Based Molecular Dynamics
- Ausgabe der Zeitschrift
- 47
Data source: Crossref
- Abstract
- CONSPECTUS: All-atom methods treat solute and solvent at the same level of electronic structure theory and statistical mechanics. All-atom computation of acidity constants (pKa) and redox potentials is still a challenge. In this Account, we review such a method combining density functional theory based molecular dynamics (DFTMD) and free energy perturbation (FEP) methods. The key computational tool is a FEP based method for reversible insertion of a proton or electron in a periodic DFTMD model system. The free energy of insertion (work function) is computed by thermodynamic integration of vertical energy gaps obtained from total energy differences. The problem of the loss of a physical reference for ionization energies under periodic boundary conditions is solved by comparing with the proton work function computed for the same supercell. The scheme acts as a computational hydrogen electrode, and the DFTMD redox energies can be directly compared with experimental redox potentials. Consistent with the closed shell nature of acid dissociation, pKa estimates computed using the proton insertion/removal scheme are found to be significantly more accurate than the redox potential calculations. This enables us to separate the DFT error from other sources of uncertainty such as finite system size and sampling errors. Drawing an analogy with charged defects in solids, we trace the error in redox potentials back to underestimation of the energy gap of the extended states of the solvent. Accordingly the improvement in the redox potential as calculated by hybrid functionals is explained as a consequence of the opening up of the bandgap by the Hartree-Fock exchange component in hybrids. Test calculations for a number of small inorganic and organic molecules show that the hybrid functional implementation of our method can reproduce acidity constants with an uncertainty of 1-2 pKa units (0.1 eV). The error for redox potentials is in the order of 0.2 V.
- Addresses
- Department of Chemistry, University of Aberdeen , Aberdeen AB24 3UE, United Kingdom.
- Autoren
- Jun Cheng
- Xiandong Liu
- Joost VandeVondele
- Marialore Sulpizi
- Michiel Sprik
- DOI
- 10.1021/ar500268y
- eISSN
- 1520-4898
- Externe Identifier
- PubMed Identifier: 25365148
- Funding acknowledgements
- Royal Society:
- British Academy:
- National Natural Science Foundation of China: 41273074
- National Natural Science Foundation of China: 41222015
- Engineering and Physical Sciences Research Council: EP/K014560/1
- Ministry of Education of the People's Republic of China: 201228
- Emmanuel College, University of Cambridge:
- Open access
- false
- ISSN
- 0001-4842
- Ausgabe der Veröffentlichung
- 12
- Zeitschrift
- Accounts of chemical research
- Sprache
- eng
- Medium
- Print-Electronic
- Online publication date
- 2014
- Paginierung
- 3522 - 3529
- Datum der Veröffentlichung
- 2014
- Status
- Published
- Datum der Datenerfassung
- 2014
- Titel
- Redox potentials and acidity constants from density functional theory based molecular dynamics.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 47
Data source: Europe PubMed Central
- Abstract
- CONSPECTUS: All-atom methods treat solute and solvent at the same level of electronic structure theory and statistical mechanics. All-atom computation of acidity constants (pKa) and redox potentials is still a challenge. In this Account, we review such a method combining density functional theory based molecular dynamics (DFTMD) and free energy perturbation (FEP) methods. The key computational tool is a FEP based method for reversible insertion of a proton or electron in a periodic DFTMD model system. The free energy of insertion (work function) is computed by thermodynamic integration of vertical energy gaps obtained from total energy differences. The problem of the loss of a physical reference for ionization energies under periodic boundary conditions is solved by comparing with the proton work function computed for the same supercell. The scheme acts as a computational hydrogen electrode, and the DFTMD redox energies can be directly compared with experimental redox potentials. Consistent with the closed shell nature of acid dissociation, pKa estimates computed using the proton insertion/removal scheme are found to be significantly more accurate than the redox potential calculations. This enables us to separate the DFT error from other sources of uncertainty such as finite system size and sampling errors. Drawing an analogy with charged defects in solids, we trace the error in redox potentials back to underestimation of the energy gap of the extended states of the solvent. Accordingly the improvement in the redox potential as calculated by hybrid functionals is explained as a consequence of the opening up of the bandgap by the Hartree-Fock exchange component in hybrids. Test calculations for a number of small inorganic and organic molecules show that the hybrid functional implementation of our method can reproduce acidity constants with an uncertainty of 1-2 pKa units (0.1 eV). The error for redox potentials is in the order of 0.2 V.
- Autoren
- Jun Cheng
- Xiandong Liu
- Joost VandeVondele
- Marialore Sulpizi
- Michiel Sprik
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/25365148
- DOI
- 10.1021/ar500268y
- eISSN
- 1520-4898
- Ausgabe der Veröffentlichung
- 12
- Zeitschrift
- Acc Chem Res
- Sprache
- eng
- Country
- United States
- Paginierung
- 3522 - 3529
- Datum der Veröffentlichung
- 2014
- Status
- Published
- Datum, an dem der Datensatz öffentlich gemacht wurde
- 2015
- Titel
- Redox potentials and acidity constants from density functional theory based molecular dynamics.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 47
Data source: PubMed
- Beziehungen:
-