Study of electron transfer at semiconductor-liquid interfaces addressing the full system electronic structure

Smith, B. Babington; Nozik, Arthur J.

doi:10.1016/0301-0104(95)00315-0

Cited by 40 publications

(67 citation statements)

References 23 publications

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“…Energies of these states are tuned by the solvent and the electrode and form a complex distribution of probabilities. 51,53 Even though some experimental features are not reproduced effectively in the simulation, the model enables a straightforward extraction of rate constants from simple cyclic voltammetry experiments. Figure 4B compares k f and k b values obtained for HBC and CQD electrodes.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Electron Transfer Kinetics at Graphene Quantum Dot Assembly Electrodes

Zoric

Singh

Warren

et al. 2019

ACS Appl. Mater. Interfaces

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Electrochemical performance of nanostructured carbon electrodes was evaluated using cyclic voltammetry and a simple simulation model. The electrodes were prepared from soluble precursors by anodic electrodeposition of two sizes of graphene quantum dot assemblies (hexabenzocoronene (HBC) and carbon quantum dot (CQD)) onto a conductive support. Experimental and simulated voltammograms enabled the extraction of the following electrode parameters: conductivity of the electrodes (a combination of ionic and electronic contributions), density of available electrode states at different potentials, and tunneling rate constant (Marcus−Gerischer model) for interfacial charge transfer to ferrocene/ferrocenium (Fc/Fc + ) couple. The parameters indicate that HBC and CQD have significant density of electronic states at potentials more positive than −0.5 V versus Ag/Ag + . Enabled by these large densities, the electron transfer rates at the Fc/Fc + thermodynamic potential are several orders of magnitude slower than those commonly observed on other carbon electrodes. This study is expected to accelerate the discovery of improved synthetic carbon electrodes by providing fast screening methodology of their electrochemical behavior.

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Section: ■ Results and Discussionmentioning

confidence: 99%

“…To improve the match, simulated Gaussian probabilities, W ox and W red , would need to be replaced by the more complex manifold of Fc and Fc + orbitals that are available for charge transfer. Energies of these states are tuned by the solvent and the electrode and form a complex distribution of probabilities. , …”

Section: Resultsmentioning

confidence: 99%

Electron Transfer Kinetics at Graphene Quantum Dot Assembly Electrodes

Zoric

Singh

Warren

et al. 2019

ACS Appl. Mater. Interfaces

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“…But one would still expect a distribution of occupied and unoccupied states around the Fermi level. Knowing this density of states is a central ingredient of understanding charge transfer processes as was recently discussed in a theoretical paper calculating the interfacial electronic structure …”

Section: Discussionmentioning

confidence: 99%

Synchrotron-Induced Photoelectron Spectroscopy of Semiconductor/Electrolyte Model Interfaces: Coadsorption of Br₂ and H₂O on WSe₂(0001)

1996

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Semiconductor/electrolyte model interfaces are prepared in UHV by coadsorbing the redox active electrolyte species Br 2 and the solvent H 2 O onto chemically inert van der Waals (0001) surfaces of WSe 2 . Only a small fraction of the adsorbed Br 2 is ionosorbed due to charge exchange with the semiconductor bulk; most of it and H 2 O are molecularly adsorbed. Thus the observed changes of band bending and work function are related to charge transfer processes at the interface to achieve electronic equilibrium. The value of band bending obtained for the model electrolyte is in reasonable agreement to the equivalent Volta potential of the electrolyte contact. For the Br 2 /H 2 O coadsorption system it is only determined by Br 2 and not affected by coadsorbed H 2 O. In addition, the relative density of state distribution of the semiconductor and the model electrolyte can directly be determined from the electron distribution curve of the valence band region and compared to theoretical expectations of electrolyte interfaces. We observe for Br 2 and H 2 O adsorbates remarkable discrepancies to established electrochemical theories, which in part is attributed to the multielectron nature of the redox couples.

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“…This situation is obviously different than when this same time dependence is used for the homogeneous case (eq 8), since for the SLI case the electronic coupling is turned on the entire time the state is in the conduction band and the ET is characterized by irreversibility. The α in eq 10 is chosen so that the increase and decrease occur at a rate consistent with typical SLI solvent dynamics (we have investigated this elsewhere, , and we find so far that the transition state lifetime, τ TS , can vary on average from about 10−1000 fs for various regimes and SLI systems). Figure shows that as the time spent by ε RET in the conduction band (essentially the transition state lifetime, τ TS ) increases relative to the approximate lifetime of the redox species electronic state (τ EL ) ℙ increases (the long time n REDOX decreases).…”

Section: Sli Et (1d Models)mentioning

confidence: 99%

A Wave Packet Model for Electron Transfer and Its Implications for the Semiconductor−Liquid Interface

and

Nozik

1999

J. Phys. Chem. B

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This paper establishes the computational feasibility and examines the implications of a particular technique for simulations of time dependent electron transfer (ET) at semiconductor-liquid interfaces (SLIs). The methodology uses a one electron formalism employing wave packets, pseudopotentials, and molecular dynamics, which we dub WPMD. We describe a detailed mechanism for SLI ET by using the methodology. The model is versatile enough to address conventional SLI ET, surface state and adsorption mediated ET, photoexcited ET, and ET between quantum dots and other microstructures. We contrast the perspectives of our WPMD model of SLI ET with those in traditional literature and find substantial differences. The use of standard Landau-Zener theory for SLI ET is found particularly problematic.

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Study of electron transfer at semiconductor-liquid interfaces addressing the full system electronic structure

Cited by 40 publications

References 23 publications

Electron Transfer Kinetics at Graphene Quantum Dot Assembly Electrodes

Electron Transfer Kinetics at Graphene Quantum Dot Assembly Electrodes

Synchrotron-Induced Photoelectron Spectroscopy of Semiconductor/Electrolyte Model Interfaces: Coadsorption of Br₂ and H₂O on WSe₂(0001)

A Wave Packet Model for Electron Transfer and Its Implications for the Semiconductor−Liquid Interface

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Study of electron transfer at semiconductor-liquid interfaces addressing the full system electronic structure

Cited by 40 publications

References 23 publications

Electron Transfer Kinetics at Graphene Quantum Dot Assembly Electrodes

Electron Transfer Kinetics at Graphene Quantum Dot Assembly Electrodes

Synchrotron-Induced Photoelectron Spectroscopy of Semiconductor/Electrolyte Model Interfaces: Coadsorption of Br2 and H2O on WSe2(0001)

A Wave Packet Model for Electron Transfer and Its Implications for the Semiconductor−Liquid Interface

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Product

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Synchrotron-Induced Photoelectron Spectroscopy of Semiconductor/Electrolyte Model Interfaces: Coadsorption of Br₂ and H₂O on WSe₂(0001)