Two-step model for ultrafast interfacial electron transfer: limitations of Fermi’s golden rule revealed by quantum dynamics simulations

Abstract

A two-step model of interfacial electron transfer is proposed along with a practical approach to screening dye-sensitizers based on a calculation of the percentage of electron density on the linker group and the number of available semiconductor acceptor states.

HOMO inversion as a strategy for improving the light-absorption properties of Fe(ii) chromophores

“…The increases in the LUMO energy and density on the carboxylic acid linker are lower than those for 1h (0.31 eV and 1.9%, respectively) but higher than for 1c (0 eV and –0.5%, respectively). As higher electron density on the carboxylic acid linker and higher LUMO energy are some of the important parameters for efficient IET, 37 , 56 , 60 we predict that the IET efficiency from the excited states populating the LUMOs of these complexes will follow the order of 1h > 1c′′′′ > 1c .…”

“…, achieve strong and broad absorption in the visible and near-IR region). A strong link between the electronic structure of the dyes, especially the amount of electron density on the semiconductor linker group in the excited state, and the initial IET rates 56 , 60 also allows us to explore the impact of the ligand modifications on the IET efficiency, albeit to a smaller (and less reliable) extent.…”

Toward Large‐Scale Hydrogen Production from Water: What Have We Learned and What Are the Main Research Hurdles to Cross for Commercialization?

“…Computation based on time‐dependent (TD) ab initio methods (TD‐DFT, [ 91 ] perturbation theory–based, and other methods [ 92,93 ] ) for solid state studies are also needed so information related to interfacial charge transfer, charge carriers lifetime, and excited energy states can complement experimental results. [ 94,95 ] In particular, the problem of hole localization, which is linked to the surface structure and associated energy position, has been discussed and some attempts made to model the energy profile of both excited electron and hole TR signal using TD‐DFT.…”

Effect of ligand groups on photoexcited charge carrier dynamics at the perovskite/TiO2 interface

“…27 Certain materials have shown the ability to accept these separated charges from the perovskite when placed in contact with the perovskite. [28][29][30] This increases the efficiency of charge separation and extraction, thereby improving the power conversion efficiency (PCE) of perovskite-based photovoltaic devices. 31 Materials that accept electrons have been dubbed electron transport materials (ETMs) and hole accepting materials are likewise called hole transport materials (HTMs).…”

“…There is ongoing research into the origin of the hysteretic behavior of their I-V curves 1 as well as the ultrafast (<1 ps) charge injection into ETMs/HTMs. [28][29][30] This work focuses on the effects of ligands adsorbed to a POT ETM. More specically, the ground state properties and photoexcited charge carrier dynamics of two different perovskite/ETM structures are explored.…”