Estimation of inner shell Marcus terms for amino nitrogen compounds by molecular orbital calculations

Nelsen, Stephen F.; Blackstock, Silas C.; Kim, Yaesil

doi:10.1021/ja00237a007

Cited by 454 publications

(443 citation statements)

References 0 publications

Supporting

Mentioning

437

Contrasting

Unclassified

Order By: Relevance

“…Both site energies and transfer integrals were calculated with the Turbomole package [26] [27] and a def2-SV(P) basis set [28]. The electron and hole reorganization energies of molecules in this box were calculated using Nelsen's four-point-procedure [29] with a B3LYP functional and a def2-TZVP basis set in TURBOMOLE [30].…”

Section: Ab Initio Calculations and Stochastic Expansion Methodsmentioning

confidence: 99%

Effects of energy correlations and superexchange on charge transport and exciton formation in amorphous molecular semiconductors: An ab initio study

et al. 2017

View full text Add to dashboard Cite

Massé, A.; Friederich, P.; Symalla, F.; Liu, F.; Meded, V.; Coehoorn, R.; Wenzel, W.; Bobbert, P.A. Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers)Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication Citation for published version (APA):Massé, A., Friederich, P., Symalla, F., Liu, F., Meded, V., Coehoorn, R., ... Bobbert, P. A. (2017). Effects of energy correlations and superexchange on charge transport and exciton formation in amorphous molecular semiconductors: an ab initio study. Physical Review B, 95(11), 1-11. [115204]. DOI: 10.1103/PhysRevB.95.115204 General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. In this study, we investigate on the basis of ab initio calculations how the morphology, molecular on-site energies, reorganization energies, and charge transfer integral distribution affect the hopping charge transport and the exciton formation process in disordered organic semiconductors. We focus on three materials applied frequently in organic light-emitting diodes: α-NPD, TCTA, and Spiro-DPVBi. Spatially correlated disorder and, more importantly, superexchange contributions to the transfer integrals, are found to give rise to a significant increase of the electric field dependence of the electron and hole mobility. Furthermore, a material-specific correlation is found between the HOMO and LUMO energy on each specific molecular site. For α-NPD and TCTA, we find a positive correlation between the HOMO and LUMO energies, dominated by a Coulombic contribution to the energies. In contrast, Spiro-DPVBi shows a negative correlation, dominated by a conformational contribution. The size and sign of this correlation have a strong...

show abstract

Section: Ab Initio Calculations and Stochastic Expansion Methodsmentioning

confidence: 99%

Effects of energy correlations and superexchange on charge transport and exciton formation in amorphous molecular semiconductors: An ab initio study

et al. 2017

View full text Add to dashboard Cite

show abstract

“…This energy gap can also be calculated exactly with PBE-GGA using the "4-point" approach [29], provided that all long-range electrostatic interactions are screened out. The four calculations involve Fe 2+ in two Fe(H 2 O) 6 geometries (A and B), and Fe 3+ in the same geometries; the energy gap is…”

mentioning

confidence: 99%

Realistic Quantitative Descriptions of Electron Transfer Reactions: Diabatic Free-Energy Surfaces from First-Principles Molecular Dynamics

2006

View full text Add to dashboard Cite

A general approach to calculate the diabatic surfaces for electron-transfer reactions is presented, based on first-principles molecular dynamics of the active centers and their surrounding medium. The excitation energy corresponding to the transfer of an electron at any given ionic configuration (the Marcus energy gap) is accurately assessed within ground-state density-functional theory via a novel penalty functional for oxidation-reduction reactions that appropriately acts on the electronic degrees of freedom alone. The self-interaction error intrinsic to common exchange-correlation functionals is also corrected by the same penalty functional. The diabatic free-energy surfaces are then constructed from umbrella sampling on large ensembles of configurations. As a paradigmatic case study, the self-exchange reaction between ferrous and ferric ions in water is studied in detail.A wide variety of processes and reactions in electrochemistry, molecular electronics, and biochemistry have a common denominator: they involve a diabatic electron transfer process from a donor to an acceptor [1]. These reactions cover processes and applications as diverse as solar-energy conversion in the early steps of photosynthesis, oxidation-reduction reactions between a metallic electrode and solvated ions, and the I-V characteristics of molecular-electronics devices [2]. The key quantities of interest are the reaction rates (or, equivalently, the conductance) and the reaction pathways. Reaction rates, in the general scenario of Marcus theory [3,4,5], have a thermodynamic contribution (the classical Franck-Condon factor, broadly related to the free energy cost of a nuclear fluctuation that makes the donor and the acceptor levels degenerate in energy), and an electronic-structure, tunneling contribution (the LandauZener term, related to the overlap of the initial and final states).We argue in the following that state-of-the-art firstprinciples molecular dynamics calculations, together with several algorithmic and conceptual advances, are able to describe with quantitative accuracy these diabatic processes, while including the realistic description of the complex environment encountered, e.g. in nanoscale devices or at the interface between molecules and metals. Fig. 1 shows schematically an electron-transfer process and the free-energy diabatic surfaces according to the picture that was pioneered by Marcus [3,4,6,7]. In a polar solvent, the electron transfer process is mediated by thermal fluctuations of the solvent molecules. In the reactant state, the transferring electron is trapped at the donor site by solvent polarization; transfer might occur when the electron donor and acceptor sites become degenerate due to the thermal fluctuations of the solvent molecules. To characterize the role of the solvent on the electron-transfer reaction, a reaction coordinate ǫ for a given ionic configuration is introduced, as the energy dif- ference between the product and reactant state at that configuration [8]. This definition of reaction coordinate...

show abstract

“…The reorganization energy has two components, the internal (λi) and solvent (λs) reorganization energy: λ = λi + λs (5) The internal reorganization energies λi were computed using separate fragments by means of the Nelsen four point method [9] λi…”

Section: Resultsmentioning

confidence: 99%

Distal [FeS]-Cluster Coordination in [NiFe]-Hydrogenase Facilitates Intermolecular Electron Transfer

Petrenko¹,

Stein²

2017

Preprint

View full text Add to dashboard Cite

Biohydrogen is a versatile energy carrier for the generation of electric energy from renewable sources. Hydrogenases can be used in enzymatic fuel cells to oxidize dihydrogen. The rate of electron transfer (ET) at the anodic side between the [NiFe]-hydrogenase enzyme distal ironsulfur cluster and the electrode surface can be described by the Marcus equation. All parameters for the Marcus equation are accessible from DFT calculations. The distal cubane FeS-cluster has a three cysteine and one histidine coordination [Fe4S4](His)(Cys)3 first ligation sphere. The reorganization energy (inner-and outer-sphere) is almost unchanged upon a histidine-to-cysteine substitution. Differences in rates of electron transfer between the wild-type enzyme and the all-cysteine mutant can be rationalized by a diminished electronic coupling between the donor and acceptor molecules in the [Fe4S4](Cys)4 case. The fast and efficient electron transfer from the distal iron-sulfur cluster is realized by a fine-tuned protein environment which facilitates the flow of electrons. This study enables the design and control of electron transfer rates and pathways by protein engineering.

show abstract

Estimation of inner shell Marcus terms for amino nitrogen compounds by molecular orbital calculations

Cited by 454 publications

References 0 publications

Effects of energy correlations and superexchange on charge transport and exciton formation in amorphous molecular semiconductors: An ab initio study

Effects of energy correlations and superexchange on charge transport and exciton formation in amorphous molecular semiconductors: An ab initio study

Realistic Quantitative Descriptions of Electron Transfer Reactions: Diabatic Free-Energy Surfaces from First-Principles Molecular Dynamics

Distal [FeS]-Cluster Coordination in [NiFe]-Hydrogenase Facilitates Intermolecular Electron Transfer

Contact Info

Product

Resources

About