Diabatic model for electrochemical hydrogen evolution based on constrained DFT configuration interaction

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dc.contributor Aalto-yliopisto fi
dc.contributor Aalto University en
dc.contributor.author Holmberg, Nico
dc.contributor.author Laasonen, Kari
dc.date.accessioned 2018-10-02T11:31:12Z
dc.date.available 2018-10-02T11:31:12Z
dc.date.issued 2018-09-11
dc.identifier.citation Holmberg , N & Laasonen , K 2018 , ' Diabatic model for electrochemical hydrogen evolution based on constrained DFT configuration interaction ' JOURNAL OF CHEMICAL PHYSICS , vol 149 , no. 10 , 104702 . DOI: 10.1063/1.5038959 en
dc.identifier.issn 0021-9606
dc.identifier.issn 1089-7690
dc.identifier.other PURE UUID: 919d681a-844e-4673-9cd6-0ccfc0677807
dc.identifier.other PURE ITEMURL: https://research.aalto.fi/en/publications/diabatic-model-for-electrochemical-hydrogen-evolution-based-on-constrained-dft-configuration-interaction(919d681a-844e-4673-9cd6-0ccfc0677807).html
dc.identifier.other PURE FILEURL: https://research.aalto.fi/files/27840672/Holmberg_JCP2018_accepted.pdf
dc.identifier.uri https://aaltodoc.aalto.fi/handle/123456789/34126
dc.description.abstract The accuracy of density functional theory (DFT) based kinetic models for electrocatalysis is diminished by spurious electron delocalization effects, which manifest as uncertainties in the predicted values of reaction and activation energies. In this work, we present a constrained DFT (CDFT) approach to alleviate overdelocalization effects in the Volmer-Heyrovsky mechanism of the hydrogen evolution reaction (HER). This method is applied a posteriori to configurations sampled along a reaction path to correct their relative stabilities. Concretely, the first step of this approach involves describing the reaction in terms of a set of diabatic states that are constructed by imposing suitable density constraints on the system. Refined reaction energy profiles are then recovered by performing a configuration interaction (CDFT-CI) calculation within the basis spanned by the diabatic states. After a careful validation of the proposed method, we examined HER catalysis on open-ended carbon nanotubes and discovered that CDFT-CI increased activation energies and decreased reaction energies relative to DFT predictions. We believe that a similar approach could also be adopted to treat overdelocalization effects in other electrocatalytic proton-coupled electron transfer reactions, e.g., in the oxygen reduction reaction. en
dc.format.extent 15
dc.format.mimetype application/pdf
dc.language.iso en en
dc.relation.ispartofseries JOURNAL OF CHEMICAL PHYSICS en
dc.relation.ispartofseries Volume 149, issue 10 en
dc.rights openAccess en
dc.subject.other 215 Chemical engineering en
dc.title Diabatic model for electrochemical hydrogen evolution based on constrained DFT configuration interaction en
dc.type A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä fi
dc.description.version Peer reviewed en
dc.contributor.department School services, CHEM
dc.contributor.department Department of Chemistry and Materials Science
dc.subject.keyword 215 Chemical engineering
dc.identifier.urn URN:NBN:fi:aalto-201810025209
dc.identifier.doi 10.1063/1.5038959
dc.type.version acceptedVersion

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