Influence of polar medium on the reorganization energy of charge transfer between dyes in a dye sensitized film

Vaissier, Valérie; Barnes, Piers R. F.; Kirkpatrick, James; Nelson, Jenny

doi:10.1039/c3cp44562c

Cited by 93 publications

(107 citation statements)

References 40 publications

Supporting

Mentioning

103

Contrasting

Unclassified

Order By: Relevance

“…More detailed consideration can be found in our earlier work. 25,26 Furthermore, we calculated λ i for a specific configuration of the dye molecules.…”

Section: Calculation Of the Reorganization Energy Of Hole Exchange Bementioning

confidence: 99%

Influence of Intermolecular Interactions on the Reorganization Energy of Charge Transfer between Surface-Attached Dye Molecules

et al. 2015

Self Cite

View full text Add to dashboard Cite

The parameters controlling the kinetics of intermolecular charge transfer are traditionally estimated from electronic structure calculations on the charge donor and charge acceptor in isolation. Here, we show that this procedure results in inaccuracies for hole transfer between a pair of organic dye molecules by comparing charge-constrained density functional theory (DFT) calculations on a dye cation/neutral dye pair to the conventional DFT calculations on the isolated molecules. We quantify the error made in the reorganization energy of hole exchange between dye molecules (λ i ). We choose three indolene-based organic dyes with application to dye-sensitized solar cells, namely, D149, D102, and D131, for which experimental values of λ are available. We find that, although highly system dependent, the intermolecular interaction between the charge donor and acceptor can lead to a 0.25 eV change in λ i , illustrating the limitations of the widely used original method in predicting the rate of charge transfer.

show abstract

“…More detailed consideration can be found in our earlier work. 25,26 Furthermore, we calculated λ i for a specific configuration of the dye molecules.…”

Section: Calculation Of the Reorganization Energy Of Hole Exchange Bementioning

confidence: 99%

Influence of Intermolecular Interactions on the Reorganization Energy of Charge Transfer between Surface-Attached Dye Molecules

et al. 2015

Self Cite

View full text Add to dashboard Cite

show abstract

“…Fig. 3 Comparison of the outer-sphere reorganization energy calculated here in acetonitrile and the outer-sphere reorganisation energy calculated as in reference 6 .…”

Section: Validationmentioning

confidence: 99%

“…Within this formalism, the outer-sphere reorganisation energy will depend directly on the polarity of the solvent. 5,6 In one of his early papers, Marcus used classical electrostatics to express λ o as a function of the Pekar factor, difference between the inverse static and optical dielectric constant of the medium (ε −1 op − ε −1 r ). 1,4,7 This is a means to account for the slow (inertial with ε r ) and fast (electronic with ε op ) response of the medium to the charge transfer.…”

Section: Introductionmentioning

confidence: 99%

Influence of a nearby substrate on the reorganization energy of hole exchange between dye molecules

Manke

Frost

Vaissier

et al. 2015

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

A numerical method is presented to estimate the influence of a nearby substrate on the polarization energy and outer sphere reorganization energy (λ o ) for intermolecular hole transfer for a series of dye molecules. The calculation considers the net charge distribution of the oxidised molecule (determined from quantum chemical calculation of the highest occupied molecular orbital of the neutral molecule within the frozen orbital approximation) encapsulated within a conformal cavity, by the molecules total electron density. An analytical point charge approximation was used at longer range. The molecular cavity was either surrounded by a single polarizable continuum, or, to simulate a nearby substrate, embedded at different positions relative to the interface between two semi-infinite slabs with different dielectric constants. The calculated λ o values in the single dielectric medium were linearly related to the outer-sphere reorganisation energy calculated from DFT with a polarizable continuum model, validating the approach. In the two phase system, variations in λ o was sensitive to the position of the substrate relative to the molecule and differences in the Pekar factor (1/ε o − 1/ε r ) for the media. For dye molecules in ACN positioned touching a TiO 2 substrate λ o was typically about 20 % lower than in pure ACN depending on the molecular configuration. Our approach can be adapted to systems of more than two media.

show abstract

“…Hence nonadiabatic electron transfer with even weaker electronic coupling is expected for electron self-exchange of molecules immobilized and site isolated on oxide surfaces, H AB ≪ kT. 9 Adiabatic pathways may become operative under conditions when the molecules aggregate. 10 One would also anticipate that H AB could be controlled experimentally and systematically by varying the surface coverage and hence the intermolecular distance R over which self-exchange occurs.…”

Section: Introductionmentioning

confidence: 99%

Lateral Intermolecular Self-Exchange Reactions for Hole and Energy Transport on Mesoporous Metal Oxide Thin Films

Meyer

2015

Langmuir

View full text Add to dashboard Cite

Intermolecular self-exchange energy and electron-transfer reactions occur without a loss of free energy. This behavior can be exploited for energy-transport applications when molecules that undergo self-exchange transfer reactions are immobilized on a solid support. This Article focuses upon lateral self-exchange reactions and the relevant interfacial chemistry that occurs on the mesoporous nanocrystalline (anatase) TiO2 thin films that are commonly used in dye-sensitized solar cells. It has been known for some time that all of the dye molecules (termed sensitizers) within such thin films can be reversibly oxidized and reduced by lateral self-exchange electron transfer provided that the sensitizer surface coverage exceeds a percolation threshold. Under conditions where excited-state electron injection into TiO2 is unfavored, lateral intermolecular energy-transfer reactions are also known to occur. The self-exchange rate constants have been quantified by electrochemical, absorption, and/or time-resolved anisotropy techniques and understood within the framework of Marcus theory. Such analysis reveals that the reorganization energy and the electronic coupling are sensitive to the identity of the molecular compound. Time-resolved anisotropy measurements have shown that lateral charge and energy-transfer reactions across the TiO2 surface occur in kinetic competition with charge recombination and excited-state relaxation, respectively. The extent to which lateral self-exchange reactions might be exploited for solar energy conversion applications is discussed, as are critical fundamental issues that remain unresolved.

show abstract

Influence of polar medium on the reorganization energy of charge transfer between dyes in a dye sensitized film

Cited by 93 publications

References 40 publications

Influence of Intermolecular Interactions on the Reorganization Energy of Charge Transfer between Surface-Attached Dye Molecules

Influence of Intermolecular Interactions on the Reorganization Energy of Charge Transfer between Surface-Attached Dye Molecules

Influence of a nearby substrate on the reorganization energy of hole exchange between dye molecules

Lateral Intermolecular Self-Exchange Reactions for Hole and Energy Transport on Mesoporous Metal Oxide Thin Films

Contact Info

Product

Resources

About