Regarding the validity of the time-dependent Kohn-Sham approach for electron-nuclear dynamics via trajectory surface hopping.

The implementation of fewest-switches surface-hopping (FSSH) within time-dependent Kohn-Sham (TDKS) theory [Phys. Rev. Lett.

Ab initio nonadiabatic molecular dynamics of wet-electrons on the TiO(2) surface.

The electron transfer (ET) dynamics of wet-electrons on a TiO(2) surface is investigated using state-of-the-art ab initio nonadiabatic (NA) molecular dynamics (MD). The simulations directly mimic the time-resolved experiments [Science 2005, 308, 1154] and reveal the nature of ET in the wet-electron system. Focusing on the partially hydroxylated TiO(2) surface with 1-monolayer water coverage, and including electronic evolution, phonon motions, and electron-phonon coupling, the simulations indicate that the ET is sub-10 fs, in agreement with the experiment.

Temperature independence of the photoinduced electron injection in dye-sensitized TiO2 rationalized by ab initio time-domain density functional theory.

Time-domain density functional theory simulations resolve the apparent conflict between the central role that thermal fluctuations play in the photoinduced chromophore-TiO 2 electron transfer (ET) in dye-sensitized semiconductor solar cells [J. Am. Chem.

Dynamics of the photoexcited electron at the chromophore-semiconductor interface.

Electron dynamics at molecular-bulk interfaces play a central role in a number of different fields, including molecular electronics and sensitized semiconductor solar cells. Describing electron behavior in these systems is difficult because it requires a union between disparate interface components, molecules and solid-state materials, that are studied by two different communities, chemists and physicists, respectively. This Account describes recent theoretical efforts to bridge that gap by analyzing systems that serve as good general models of the interfacial electron dynamics.

Theoretical studies of photoinduced electron transfer in dye-sensitized TiO2.

This review describes recent research into the properties of the chromophore-TiO2 interface that forms the basis for photoinduced charge separation in dye-sensitized semiconductor solar cells. It focuses particularly on an atomistic picture of the electron-injection dynamics. The interface offers an excellent case study, pertinent as well to a variety of other photovoltaic systems, photo- and electrochemistry, molecular electronics, analytical detection, photography, and quantum confinement devices.

Nonadiabatic molecular dynamics study of electron transfer from alizarin to the hydrated Ti4+ ion.

Ab initio real-time nonadiabatic (NA) molecular dynamics (MD) simulations are performed in order to investigate the photoinduced electron transfer (ET) from alizarin to the hydrated Ti4+ ion and compare it with the ET into bulk TiO2 that forms the basis of the Grätzel type solar cell. The experimental data and electronic structure calculations indicate that the photoexcitation spectra of alizarin attached to either bulk TiO2 or the Ti4+ ion in solution are very similar. In contrast, the NAMD simulations at ambient temperature predict marked differences between the ET dynamics that follow the photoexcitation in the two systems.

Electronic structure and spectra of catechol and alizarin in the gas phase and attached to titanium.

Ab initio electronic structure calculations elucidate the dramatic differences observed in the electronic spectra of the catechol and alizarin molecules upon binding to titanium. Catechol and alizarin are similar chromophores with analogous electronic spectra in the free state. Binding alizarin to titanium red-shifts the spectrum.

Trajectory surface hopping in the time-dependent Kohn-Sham approach for electron-nuclear dynamics.

The mean-field treatment of electron-nuclear interaction results in many qualitative breakdowns in the time-dependent Kohn-Sham (TDKS) density functional theory. Examples include current-induced heating in nanoelectronics, charge dynamics in quantum dots and carbon nanotubes, and relaxation of biological chromophores. The problem is resolved by the trajectory surface-hopping TDKS approach, which is illustrated by the photoinduced electron injection from a molecular chromophore into TiO2, and the excited-state relaxation of the green fluorescent protein chromophore.

Ab initio nonadiabatic molecular dynamics of the ultrafast electron injection across the alizarin-TiO2 interface.

The observed 6-fs photoinduced electron transfer (ET) from the alizarin chromophore into the TiO2 surface is investigated by ab initio nonadiabatic (NA) molecular dynamics in real time and at the atomistic level of detail. The system derives from the dye-sensitized semiconductor Grätzel cell and addresses the problems of an organic/inorganic interface that are commonly encountered in photovoltaics, photochemistry, and molecular electronics. In contrast to the typical Grätzel cell systems, where molecular donors are in resonance with a high density of semiconductor acceptor states, TiO2 sensitized with alizarin presents a novel case in which the molecular photoexcited state is at the edge of the conduction band (CB).

Synthesis, Structure, and Properties of a Model for Galactose Oxidase.

An active-site analog of the radical copper enzyme galactose oxidase has been prepared from a synthetic tripod chelate ((2-pyridylmethyl)[(2-hydroxy-3,5-dimethylphenyl)methyl][(2-hydroxy-5-methyl-3-(methylthio)phenyl)methyl]amine, duncamine (dnc)) that binds a single Cu(II) ion through phenolate, thioether-substituted phenolate, and pyridylamine arms. The Cu complex crystallizes as a dinucleated dimer bridged by phenolate oxygens, and the structure has been determined by X-ray crystallography. Addition of pyridine (or other coordinating bases) dissociates the complex into a monomeric derivative that has been characterized spectroscopically (optical absorption and EPR) and electrochemically.