Marcus inverted region of charge transfer from low-dimensional semiconductor materials

A key process underlying the application of low-dimensional, quantum-confined semiconductors in energy conversion is charge transfer from these materials, which, however, has not been fully understood yet. Extensive studies of charge transfer from colloidal quantum dots reported rates increasing monotonically with driving forces, never displaying an inverted region predicted by the Marcus theory. The inverted region is likely bypassed by an Auger-like process whereby the excessive driving force is used to excite another Coulomb-coupled charge. Herein, instead of measuring charge transfer from excitonic states (coupled electron-hole pairs), we build a unique model system using zero-dimensional quantum dots or two-dimensional nanoplatelets and surface-adsorbed molecules that allows for measuring charge transfer from transiently-populated, single-charge states. The Marcus inverted region is clearly revealed in these systems. Thus, charge transfer from excitonic and single-charge states follows the Auger-assisted and conventional Marcus charge transfer models, respectively. This knowledge should enable rational design of energetics for efficient charge extraction from low-dimensional semiconductor materials as well as suppression of the associated energy-wasting charge recombination.

Solvation heterogeneity in ionic liquids as demonstrated by photo-chemical reactions

It has been recognised that ionic liquids (ILs) with long alkyl-chains have a segregated structure due to the inhomogeneous distribution of polar parts and non-polar parts. This inhomogeneity of ILs brings about unique solvation phenomena of solute molecules dissolved in ILs. We have investigated various solvation-state selective phenomena by using laser spectroscopic techniques such as solvation state selective vibrational spectroscopy, translational and rotational dynamics of small molecules in ILs, and solvation state selective fundamental chemical reactions. In this paper, we have reviewed an intramolecular electron transfer (ET) reaction in the Marcus inverted region of N,N-dimethyl-p-nitroaniline and an intramolecular proton transfer (IPT) reaction in 4′-N,N-diethylamino-3-hydroxyflavone as examples of chemical reactions affected by unique solvation in ILs.

Concerted proton-electron transfer reactions in the Marcus inverted region

Electron transfer reactions slow down when they become very thermodynamically favorable, a counterintuitive interplay of kinetics and thermodynamics termed the inverted region in Marcus theory. Here we report inverted region behavior for proton-coupled electron transfer (PCET). Photochemical studies of anthracene-phenol-pyridine triads give rate constants for PCET charge recombination that are slower for the more thermodynamically favorable reactions. Photoexcitation forms an anthracene excited state that undergoes PCET to create a charge-separated state. The rate constants for return charge recombination show an inverted dependence on the driving force upon changing pyridine substituents and the solvent. Calculations using vibronically nonadiabatic PCET theory yield rate constants for simultaneous tunneling of the electron and proton that account for the results.

Photoinduced bimolecular electron transfer from aromatic amines to pentafluorophenyl porphyrin combined with ultrafast charge recombination persistence with Marcus inverted region

We demonstrated intrinsic, non-stationary and diffusion controlled photo-induced bimolecular electron transfer follow Marcus inverted region.