Why DFT‐Based Tight Binding Gives a Better Representation of the Potential at Metal‐Solution Interfaces than DFT Does
Abstract In modelling electrochemical interfaces it is important to treat electrode and electrolyte at the same level of theory. Density functional theory, which is usually the method of choice, suffers from a distinct disadvantage: The inner potential is calculated as the average of the total elect...
| Main Authors: | , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley-VCH
2023-10-01
|
| Series: | ChemElectroChem |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/celc.202300230 |
| _version_ | 1797657863928152064 |
|---|---|
| author | Prof. Dr. Paola Quaino José Luis Nuñez Prof. Dr. Bálint Aradi Tammo van derHeide Prof. Dr. Elizabeth Santos Prof. Dr. Wolfgang Schmickler |
| author_facet | Prof. Dr. Paola Quaino José Luis Nuñez Prof. Dr. Bálint Aradi Tammo van derHeide Prof. Dr. Elizabeth Santos Prof. Dr. Wolfgang Schmickler |
| author_sort | Prof. Dr. Paola Quaino |
| collection | DOAJ |
| description | Abstract In modelling electrochemical interfaces it is important to treat electrode and electrolyte at the same level of theory. Density functional theory, which is usually the method of choice, suffers from a distinct disadvantage: The inner potential is calculated as the average of the total electrostatic potential. This includes the highly localized potential generated from the nuclei. The resulting inner potential is far too high, of the order of 3.5 V, and not relevant for electrochemistry. In the density functional based tight binding (DFTB) method the electrostatic potential is much smoother, as it stems from atomic charge fluctuations with respect to neutral reference atoms. The resulting values for the electrochemical inner potential are much lower and compare well with those obtained by other, elaborate methods. Thus DFTB recommends itself as a method for treating the electrochemical interface including the inner potential. |
| first_indexed | 2024-03-11T17:50:44Z |
| format | Article |
| id | doaj.art-2c6db6fe675a4241b45cfc27b588dc87 |
| institution | Directory Open Access Journal |
| issn | 2196-0216 |
| language | English |
| last_indexed | 2024-03-11T17:50:44Z |
| publishDate | 2023-10-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemElectroChem |
| spelling | doaj.art-2c6db6fe675a4241b45cfc27b588dc872023-10-18T05:39:09ZengWiley-VCHChemElectroChem2196-02162023-10-011020n/an/a10.1002/celc.202300230Why DFT‐Based Tight Binding Gives a Better Representation of the Potential at Metal‐Solution Interfaces than DFT DoesProf. Dr. Paola Quaino0José Luis Nuñez1Prof. Dr. Bálint Aradi2Tammo van derHeide3Prof. Dr. Elizabeth Santos4Prof. Dr. Wolfgang Schmickler5Instituto de Química Aplicada del Litoral (CONICET-UNL, FIQ) Universidad Nacional del Litoral Santa Fe ArgentinaInstituto de Química Aplicada del Litoral (CONICET-UNL, FIQ) Universidad Nacional del Litoral Santa Fe ArgentinaBremen Center for Computational Materials Science University of Bremen, Bremen GermanyBremen Center for Computational Materials Science University of Bremen, Bremen GermanyInstitute of Theoretical Chemistry Ulm University 89069 Ulm GermanyInstitute of Theoretical Chemistry Ulm University 89069 Ulm GermanyAbstract In modelling electrochemical interfaces it is important to treat electrode and electrolyte at the same level of theory. Density functional theory, which is usually the method of choice, suffers from a distinct disadvantage: The inner potential is calculated as the average of the total electrostatic potential. This includes the highly localized potential generated from the nuclei. The resulting inner potential is far too high, of the order of 3.5 V, and not relevant for electrochemistry. In the density functional based tight binding (DFTB) method the electrostatic potential is much smoother, as it stems from atomic charge fluctuations with respect to neutral reference atoms. The resulting values for the electrochemical inner potential are much lower and compare well with those obtained by other, elaborate methods. Thus DFTB recommends itself as a method for treating the electrochemical interface including the inner potential.https://doi.org/10.1002/celc.202300230DFTinner potentialpotential of zero chargetight bindingwork function |
| spellingShingle | Prof. Dr. Paola Quaino José Luis Nuñez Prof. Dr. Bálint Aradi Tammo van derHeide Prof. Dr. Elizabeth Santos Prof. Dr. Wolfgang Schmickler Why DFT‐Based Tight Binding Gives a Better Representation of the Potential at Metal‐Solution Interfaces than DFT Does ChemElectroChem DFT inner potential potential of zero charge tight binding work function |
| title | Why DFT‐Based Tight Binding Gives a Better Representation of the Potential at Metal‐Solution Interfaces than DFT Does |
| title_full | Why DFT‐Based Tight Binding Gives a Better Representation of the Potential at Metal‐Solution Interfaces than DFT Does |
| title_fullStr | Why DFT‐Based Tight Binding Gives a Better Representation of the Potential at Metal‐Solution Interfaces than DFT Does |
| title_full_unstemmed | Why DFT‐Based Tight Binding Gives a Better Representation of the Potential at Metal‐Solution Interfaces than DFT Does |
| title_short | Why DFT‐Based Tight Binding Gives a Better Representation of the Potential at Metal‐Solution Interfaces than DFT Does |
| title_sort | why dft based tight binding gives a better representation of the potential at metal solution interfaces than dft does |
| topic | DFT inner potential potential of zero charge tight binding work function |
| url | https://doi.org/10.1002/celc.202300230 |
| work_keys_str_mv | AT profdrpaolaquaino whydftbasedtightbindinggivesabetterrepresentationofthepotentialatmetalsolutioninterfacesthandftdoes AT joseluisnunez whydftbasedtightbindinggivesabetterrepresentationofthepotentialatmetalsolutioninterfacesthandftdoes AT profdrbalintaradi whydftbasedtightbindinggivesabetterrepresentationofthepotentialatmetalsolutioninterfacesthandftdoes AT tammovanderheide whydftbasedtightbindinggivesabetterrepresentationofthepotentialatmetalsolutioninterfacesthandftdoes AT profdrelizabethsantos whydftbasedtightbindinggivesabetterrepresentationofthepotentialatmetalsolutioninterfacesthandftdoes AT profdrwolfgangschmickler whydftbasedtightbindinggivesabetterrepresentationofthepotentialatmetalsolutioninterfacesthandftdoes |