Exploring excited states of Pt(ii) diimine catecholates for photoinduced charge separation

The intense absorption in the red part of the visible range, and the presence of a lowest charge-transfer excited state, render Platinum(II) diimine catecholates potentially promising candidates for light-driven applications. Here, we test their potential as sensitisers in dye-sensitised solar cells and apply, for the first time, the sensitive method of photoacoustic calorimetry (PAC) to determine the efficiency of electron injection in the semiconductor from a photoexcited Pt(II) complex. Pt(II) catecholates containing 2,2′-bipyridine-4,4′-di-carboxylic acid (dcbpy) have been prepared from their parent iso-propyl ester derivatives, complexes of 2,2′-bipyridine-4,4′-di-C(O)OiPr, (COOiPr)2bpy, and their photophysical and electrochemical properties studied. Modifying diimine Pt(II) catecholates with carboxylic acid functionality has allowed for the anchoring of these complexes to thin film TiO2, where steric bulk of the complexes (3,5-ditBu-catechol vs. catechol) has been found to significantly influence the extent of monolayer surface coverage. Dye-sensitised solar cells using Pt(dcbpy)(tBu2Cat), 1a, and Pt(dcbpy)(pCat), 2a, as sensitisers, have been assembled, and photovoltaic measurements performed. The observed low, 0.02–0.07%, device efficiency of such DSSCs is attributed at least in part to the short excited state lifetime of the sensitisers, inherent to this class of complexes. The lifetime of the charge-transfer ML/LLCT excited state in Pt((COOiPr)2bpy)(3,5-di-tBu-catechol) was determined as 250 ps by picosecond time-resolved infrared spectroscopy, TRIR. The measured increase in device efficiency for 2a over 1a is consistent with a similar increase in the quantum yield of charge separation (where the complex acts as a donor and the semiconductor as an acceptor) determined by PAC, and is also proportional to the increased surface loading achieved with 2a. It is concluded that the relative efficiency of devices sensitised with these particular Pt(II) species is governed by the degree of surface coverage. Overall, this work demonstrates the use of Pt(diimine)(catecholate) complexes as potential photosensitizers in solar cells, and the first application of photoacoustic calorimetry to Pt(II) complexes in general

Femtosecond time-resolved two-photon photoemission studies of ultrafast carrier relaxation in Cu_2O photoelectrodes

Cuprous oxide (Cu_2O) is a promising material for solar-driven water splitting to produce hydrogen. However, the relatively small accessible photovoltage limits the development of efficient Cu_2O based photocathodes. Here, femtosecond time-resolved two-photon photoemission spectroscopy has been used to probe the electronic structure and dynamics of photoexcited charge carriers at the Cu_2O surface as well as the interface between Cu_2O and a platinum (Pt) adlayer. By referencing ultrafast energy-resolved surface sensitive spectroscopy to bulk data we identify the full bulk to surface transport dynamics for excited electrons rapidly localized within an intrinsic deep continuous defect band ranging from the whole crystal volume to the surface. No evidence of bulk electrons reaching the surface at the conduction band level is found resulting into a substantial loss of their energy through ultrafast trapping. Our results uncover main factors limiting the energy conversion processes in Cu_2O and provide guidance for future material development

Performance of the CMS Cathode Strip Chambers with Cosmic Rays

The Cathode Strip Chambers (CSCs) constitute the primary muon tracking device in the CMS endcaps. Their performance has been evaluated using data taken during a cosmic ray run in fall 2008. Measured noise levels are low, with the number of noisy channels well below 1%. Coordinate resolution was measured for all types of chambers, and fall in the range 47 microns to 243 microns. The efficiencies for local charged track triggers, for hit and for segments reconstruction were measured, and are above 99%. The timing resolution per layer is approximately 5 ns

Potential of Macrostomum lignano to recover from γ-ray irradiation

Stem cells are the only proliferating cells in flatworms and can be eliminated by irradiation with no damage to differentiated cells. We investigated the effect of fractionated irradiation schemes on Macrostomum lignano, namely, on survival, gene expression, morphology and regeneration. Proliferating cells were almost undetectable during the first week post-treatment. Cell proliferation and gene expression were restored within 1 month in a dose-dependent manner following exposure to up to 150 Gy irradiation. During recovery, stem cells did not cross the midline but were restricted within lateral compartments. An accumulated dose of 210 Gy resulted in a lethal phenotype. Our findings demonstrate that M. lignano represents a suitable model system for elucidating the effect of irradiation on the stem cell system in flatworms and for improving our understanding of the recovery potential of severely damaged stem-cell systems

Performance and Operation of the CMS Electromagnetic Calorimeter

The operation and general performance of the CMS electromagnetic calorimeter using cosmic-ray muons are described. These muons were recorded after the closure of the CMS detector in late 2008. The calorimeter is made of lead tungstate crystals and the overall status of the 75848 channels corresponding to the barrel and endcap detectors is reported. The stability of crucial operational parameters, such as high voltage, temperature and electronic noise, is summarised and the performance of the light monitoring system is presented

Calibration of the CMS Drift Tube Chambers and Measurement of the Drift Velocity with Cosmic Rays

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CMS Data Processing Workflows during an Extended Cosmic Ray Run

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Aligning the CMS Muon Chambers with the Muon Alignment System during an Extended Cosmic Ray Run

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