We report a synthesis of highly luminescent (CdSe)ZnS composite quantum dots with CdSe cores ranging in diameter from 23 to 55 A. The narrow photoluminescence (fwhm ≤ 40 nm) from these composite dots spans most of the visible spectrum from blue through red with quantum yields of 30−50% at room temperature. We characterize these materials using a range of optical and structural techniques. Optical absorption and photoluminescence spectroscopies probe the effect of ZnS passivation on the electronic structure of the dots. We use a combination of wavelength dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, small and wide angle X-ray scattering, and transmission electron microscopy to analyze the composite dots and determine their chemical composition, average size, size distribution, shape, and internal structure. Using a simple effective mass theory, we model the energy shift for the first excited state for (CdSe)ZnS and (CdSe)CdS dots with varying shell thickness. Finally, we characterize the...

(CdSe)ZnS Core-Shell Quantum Dots - Synthesis and Characterization of a Size Series of Highly Luminescent Nanocrystallites

6. Rehybridization of the Acceptor (RICT) 3908 7. Planarization of the Molecule (PICT) 3909 III. Fluorescence Spectroscopy 3909 A. Solvent Effects and the Model Compounds 3909 1. Solvent Effects on the Spectra 3909 2. Steric Effects and Model Compounds 3911 3. Bandwidths 3913 4. Isoemissive Points 3914 B. Dipole Moments 3915 C. Radiative Rates and Transition Moments 3916 1. Quantum Yields and Radiationless Deactivation Processes 3916

Structural Changes Accompanying Intramolecular Electron Transfer: Focus on Twisted Intramolecular Charge-Transfer States and Structures

"United we stand, divided we fall."--Aesop. Aggregation-induced emission (AIE) refers to a photophysical phenomenon shown by a group of luminogenic materials that are non-emissive when they are dissolved in good solvents as molecules but become highly luminescent when they are clustered in poor solvents or solid state as aggregates. In this Review we summarize the recent progresses made in the area of AIE research. We conduct mechanistic analyses of the AIE processes, unify the restriction of intramolecular motions (RIM) as the main cause for the AIE effects, and derive RIM-based molecular engineering strategies for the design of new AIE luminogens (AIEgens). Typical examples of the newly developed AIEgens and their high-tech applications as optoelectronic materials, chemical sensors and biomedical probes are presented and discussed.

Aggregation-Induced Emission: The Whole Is More Brilliant than the Parts

By using bifunctional surface modifiers (SH−R−COOH), CdSe quantum dots (QDs) have been assembled onto mesoscopic TiO2 films. Upon visible light excitation, CdSe QDs inject electrons into TiO2 nanocrystallites. Femtosecond transient absorption as well as emission quenching experiments confirm the injection from the excited state of CdSe QDs into TiO2 nanoparticles. Electron transfer from the thermally relaxed s-state occurs over a wide range of rate constant values between 7.3 × 109 and 1.95 × 1011 s-1. The injected charge carriers in a CdSe-modified TiO2 film can be collected at a conducting electrode to generate a photocurrent. The TiO2−CdSe composite, when employed as a photoanode in a photoelectrochemical cell, exhibits a photon-to-charge carrier generation efficiency of 12%. Significant loss of electrons occurs due to scattering as well as charge recombination at TiO2/CdSe interfaces and internal TiO2 grain boundaries.

Quantum dot solar cells. harvesting light energy with CdSe nanocrystals molecularly linked to mesoscopic TiO2 films.

Cytochrome P450 (P450) enzymes catalyze a variety of reactions and convert chemicals to potentially reactive products as well as make compounds less toxic. Most of the P450 reactions are oxidations. The majority of these can be rationalized in the context of an FeO3+ intermediate and odd electron abstraction/rebound mechanisms; however, other iron−oxygen complexes are possible and alternate chemistries can be considered. Another issue regarding P450-catalyzed reactions is the delineation of rate-limiting steps in the catalytic cycle and the contribution to reaction selectivity. In addition to the rather classical oxidations, P450s also catalyze less generally discussed reactions including reduction, desaturation, ester cleavage, ring expansion, ring formation, aldehyde scission, dehydration, ipso attack, one-electron oxidation, coupling reactions, rearrangement of fatty acid and prostaglandin hydroperoxides, and phospholipase activity. Most of these reactions are rationalized in the context of high-valent...

Common and uncommon cytochrome P450 reactions related to metabolism and chemical toxicity.

We studied the optical transient bleaching of ∼40 A, ammonia‐passivated CdS clusters in a polymer with nanosecond and picosecond pump‐probe techniques. The transient bleaching spectra behave differently in different time regimes. Within the 30‐ps pump laser pulse width, we tentatively attribute the bleaching to the exciton‐exciton interaction, and the magnitude can be enhanced by surface passivation. On time scales of tens of picoseconds and longer following the pump pulse, when only trapped electron‐hole pairs remain from the pump excitation, the bleaching is due to the interaction between such a trapped electron‐hole pair and a bound exciton produced by the probe light. Experimentally we determined that roughly one trapped electron‐hole pair can bleach the excitonic absorption of the whole CdS cluster. We developed a theoretical model which considers the effects of the trapped electron‐hole pair on the energy of the exciton transition and its oscillator strength. We found that, when a trapped electron and hole are present, the lowest exciton absorption is red‐shifted from the original exciton absorption, and this transition has a weak oscillator strength, which explains the observed efficient bleaching. The model also predicts that a trapped electron is more efficient than a trapped hole for bleaching the excitonic absorption of CdS clusters in the size regime considered here. This is confirmed by pulse radiolysis results. Finally, we discuss the possible effects of charged surface defects on the linear absorption spectra of semiconductor clusters.

Optical transient bleaching of quantum‐confined CdS clusters: The effects of surface‐trapped electron–hole pairs

We report a picosecond pump–probe study of 55 A cadmium sulfide microcrystallites embedded in polymer films. Large negative absorbance changes at wavelengths corresponding to energies near the band gap are observed. This absorption bleaching and the associated changes in refractive index are mainly responsible for the large nonlinearity observed in degenerate four‐wave mixing experiments. Based on photoluminescence data, the known electron‐trapping cross section of defects, and these pump–probe experiments, we show that the conventional carrier density‐dependent band‐filling mechanism cannot account for the data, and the absorption bleaching is due to the saturation of the excitonic transition. We further show that the phase‐space filling and exchange effects from exciton–exciton and exciton‐free carrier interactions fail to account for the observed data. Instead, we propose that the exciton‐trapped carrier interaction is mainly responsible for the observed bleaching of the excitonic absorption. This interaction is unique for small semiconductor clusters since the presence of a high density of defects (most likely on the surfaces) causes the extremely rapid trapping of free carriers. According to this model, the recovery time of the absorption bleaching is determined by the trapped‐carrier relaxation time, which is sensitive to the fabrication methods and can be controlled by surface chemistry. Our study also demonstrates that one needs to understand the effects of surfaces and control the surface chemistry before the important question of size effects on the nonlinear optical properties can be addressed.

A picosecond bleaching study of quantum‐confined cadmium sulfide microcrystallites in a polymer film

La photochimie de α-PW 12 O 40 3− a ete etudiee dans la N-methylpyrrolidone, la tetramethyl-1,1,3,9 uree et la dimethyl-1,3imidazolidone-2. Structure aux rayons X du complexe de tungstene forme avec l'uree

Catalytic photochemical oxidation of organic substrates by polyoxometalates. Picosecond spectroscopy, photochemistry, and structural properties of charge-transfer complexes between heteropolytungstic acids and dipolar organic compounds

On etudie les complexes formes par le tetranitromethane et divers anthracenes substitues en positions 9 et 9-10 Mecanisme Cinetique

Edwin F. Hilinski

Papers

Optical transient bleaching of quantum‐confined CdS clusters: The effects of surface‐trapped electron–hole pairs

A picosecond bleaching study of quantum‐confined cadmium sulfide microcrystallites in a polymer film

Catalytic photochemical oxidation of organic substrates by polyoxometalates. Picosecond spectroscopy, photochemistry, and structural properties of charge-transfer complexes between heteropolytungstic acids and dipolar organic compounds

Reactive ion pairs from the charge-transfer excitation of electron donor-acceptor complexes

Charge-transfer excitation of electron donor-acceptor complexes. Direct observation of ion pairs by time-resolved (picosecond) spectroscopy