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Broad-band pump-probe spectroscopy combined with global and target analysis is employed to study the vibronic and excitonic dynamics of two dimers and a tetramer of perylenediimides. A simultaneous analysis is developed for two systems that have been measured in the same conditions. This enhances the resolvability of the vibronic and excitonic dynamics of the systems, and the solvent contributions that are common in the experiments. We resolve two oscillations of 1399 cm-1 or 311 cm-1 damped with ≈30/ps involved in vibrational relaxation and two more oscillations of 537 cm-1 or 136 cm-1 damped with ≈3/ps. A relaxation process with a rate of 2.1/ps-3.2/ps that is positively correlated with the excitonic coupling was discovered in all three model systems, attributed to annihilation of the one but lowest exciton state.

Bimetallic platinum complexes have interesting luminescent properties and feature long-lasting vibrational coherence and ultrafast intersystem crossing (ISC) after photoexcitation. Ultrafast triplet formation is driven by very strong spin-orbit coupling in these platinum (II) systems, where relativistic theoretical approaches beyond first-order perturbation theory are desirable. Using a fully variational relativistic theoretical method recently developed by the authors, we investigate the origins of ultrafast ISC in the [Pt(ppy) (μ-tBu2pz)]2 complex (ppy = phenylpyridine, pz = pyrazolate). Spin-orbit coupling values, evaluated along a Born-Oppenheimer molecular dynamics trajectory, are used to propagate electronic populations in time. Using this technique, we estimate ultrafast ISC rates of 15–134 fs in this species for the possible ISC pathways into the three low-lying triplet states.

High-throughput screening has been widely utilized in the pharmaceutical and manufacturing industry targeting the development of new molecules and materials for numerous applications. To enable more rapid progress in photocatalytic water-splitting reactions, the construction of high-throughput combinatorial photoreactors enabling the parallel optimization of relevant compositions under varieties of experimental conditions seems appropriate. This contribution describes a 16-photoreactor apparatus permitting the kinetic evaluation of photocatalytic gas-producing reactions using head-space pressure, gas chromatography, and mass spectrometry operating in parallel, illustrated with molecular-based homogeneous photocatalytic H2-generating compositions.

Lead zirconate titanate is a solid solution with nominal composition Pb(ZrxTi1−x)O3. Ferroelectric thin films of this material have been successfully deposited by a focused ion‐beam sputtering technique in an O2 atmosphere. These films were characterized according to composition, crystal structure, and dielectric and ferroelectric properties. The effects of deposition temperature, heat treatment after deposition, and substrate and target material were investigated. The composition of the films was within 1 at.% of the composition of the multicomponent PZT target for substrate temperatures up to 200 °C. The Pb concentration decreased for substrate temperatures above 200 °C. Films deposited at substrate temperatures below 250 °C were microcrystalline. At 300 °C, the pyrochlore phase was obtained. Films with the ferroelectric perovskite structure were deposited above 400 °C, which is the lowest deposition temperature ever reported for this phase. O2 losses during postdeposition annealing resulted in a collap...

Thin films of Cr, Mo, Ti, W, and Zr metals deposited by dc ion‐beam sputtering in noble‐gas atmospheres were found to be superconducting with transition temperatures substantially higher than those observed for the respective bulk metals. Mo films deposited with a Xe ion beam were found to be superconducting at a temperature of 7.2°K. A variation of Tc was observed for films deposited using different noble gases with highest transition temperatures obtained for deposition with Xe gas. Ion‐beam‐sputtered thin films of Nb, Ru, Ta, and V metals were similarly deposited with a resulting decrease in Tc as compared with their bulk metals. Film deposition with noble gases of higher mass produced higher Tc's than those obtained with lower‐mass noble gases. The mechanism responsible for the variation of the superconducting transition temperatures of these metal films is not known at this time but may be associated with the formation of a dilute solution/mixture of the noble gas and the transition metal, a change i...