Model car-exhaust catalyst studied by TPD and TP-RAIRS: Surface reactions of NO on clean and O-covered Ir{100}

The adsorption of NO on Ir{100} has been studied as a function of NO coverage and temperature using temperature programmed reflection absorption infrared spectroscopy (TP-RAIRS), low energy electron diffraction (LEED) and temperature programmed desorption (TPD). After saturating the clean (1 x 5)-reconstructed surface with NO at 95 K. two N-2, desorption peaks are observed upon heating. The first N-2 peak at 346 K results from the decomposition of bridge-bonded NO, and the second at 475 K from the decomposition of atop-bonded NO molecules. NO decomposition is proposed to be the rate limiting step for both N-2 desorption states. For high NO coverages on the (1 x 5) surface, the narrow width of the first N-2 desorption peak is indicative of an autocatalytic process for which the parallel formation of N2O appears to be the crucial step. When NO is adsorbed on the metastable unreconstructed (1 x 1) phase of clean Ir{100} N-2 desorption starts at lower temperatures, indicating that this surface modification is more reactive. When a high coverage of oxygen, near 0.5 ML, is pre-adsorbed on the surface, the decomposition of NO is inhibited and mainly desorption of intact NO is observed.

Excited states of nitro-polypyridine metal complexes and their ultrafast decay. Time-resolved IR absorption, spectroelectrochemistry, and TD-DFT calculations of fac-[Re(Cl)(CO)3(5-Nitro-1,10-phenanthroline)]

The lowest absorption band of fac-[Re(Cl)(CO)(3)(5-NO2-phen)] encompasses two close-lying MLCT transitions. The lower one is directed to LUMO, which is heavily localized on the NO2 group. The UV-vis absorption spectrum is well accounted for by TD-DFT (G03/PBEPBE1/CPCM), provided that the solvent, MeCN, is included in the calculations. Near-UV excitation of fac-[Re(Cl)(CO)(3)(5-NO2-phen)] populates a triplet metal to ligand charge-transfer excited state, (MLCT)-M-3, that was characterized by picosecond time-resolved IR spectroscopy. Large positive shifts of the v(CO) bands upon excitation (+70 cm(-1) for the A'(1) band) signify a very large charge separation between the Re(Cl)(CO)3 unit and the 5-NO2-phen ligand. Details of the excited-state character are revealed by TD-DFT calculated changes of electron density distribution. Experimental excited-state v(CO) wavenumbers agree well with those calculated by DFT. The (MLCT)-M-3 state decays with a ca. 10 ps lifetime (in MeCN) into another transient species, that was identified by TRIR and TD-DFT calculations as an intraligand (3)n pi* excited state, whereby the electron density is excited from the NO2 oxygen lone pairs to the pi* system of 5-NO2-phen. This state is short-lived, decaying to the ground state with a similar to 30 ps lifetime. The presence of an n pi* state seems to be the main factor responsible for the lack of emission and the very short lifetimes of 3 MLCT states seen in all d(6)-metal complexes of nitro-polypyridyl ligands. Localization of the excited electron density in the lowest (MLCT)-M-3 states parallels localization of the extra electron in the reduced state that is characterized by a very small negative shift of the v(CO) IR bands (-6 cm(-1) for A'(1)) but a large downward shift of the v(s)(NO2) IR band. The Re-Cl bond is unusually stable toward reduction, whereas the Cl ligand is readily substituted upon oxidation.

Low-lying excited states and primary photoproducts of [Os-3(CO)(10)-(s-cis-L)] (L = cyclohexa-1,3-diene, buta-1,3-diene)] clusters studied by picosecond time-resolved UV/Vis and IR spectroscopy and by density functional theory

Combined picosecond transient absorption and time-resolved infrared studies were performed, aimed at characterising low-lying excited states of the cluster [Os-3(CO)(10)(s-cis-L)] (L= cyclohexa-1,3-diene, 1) and monitoring the formation of its photoproducts. Theoretical (DFT and TD-DFT) calculations on the closely related cluster with L=buta-1,3-diene (2') have revealed that the low-lying electronic transitions of these [Os-3(CO)(10)(s-cis-1,3-diene)] clusters have a predominant sigma(core)pi*(CO) character. From the lowest sigmapi* excited state, cluster 1 undergoes fast Os-Os(1,3-diene) bond cleavage (tau=3.3 ps) resulting in the formation of a coordinatively unsaturated primary photoproduct (1a) with a single CO bridge. A new insight into the structure of the transient has been obtained by DFT calculations. The cleaved Os-Os(1,3-diene) bond is bridged by the donor 1,3-diene ligand, compensating for the electron deficiency at the neighbouring Os centre. Because of the unequal distribution of the electron density in transient la, a second CO bridge is formed in 20 ps in the photoproduct [Os-3(CO)(8)(mu-CO)(2)- (cyclohexa-1,3-diene)] (1b). The latter compound, absorbing strongly around 630 nm, mainly regenerates the parent cluster with a lifetime of about 100 ns in hexane. Its structure, as suggested by the DFT calculations, again contains the 1,3-diene ligand coordinated in a bridging fashion. Photoproduct 1b can therefore be assigned as a high-energy coordination isomer of the parent cluster with all Os-Os bonds bridged.

System performance in IR atmospheric radiometry

System aspects of filter radiometer optics used to sense planetary atmospheres are described. Thus the lenses, dichroic beamsplitters and filters in longwave channels of the Mars Observer PMIRR Pressure Modulator Infrared radiometer instrument are assessed individually, and as systems at 20.7µm, 31.9µm, 47.2µm wavelength. A window filter and a longwave calibration filter of the SCARAB earth observer instrument are assessed similarly.

Performance model for cooled IR filters

A low-temperature model is described for infrared multilayer filters containing PbTe (or other semiconductor) and ZnSe (or other II/VI). The model is based on dielectric dispersion with semiconductor carrier dispersion added. It predicts an improved performance on cooling such as would be useful to avoid erroneous signals from optics in spaceflight radiometers. Agreement with measurement is obtained over the initial temperature range 70-400K and wavelength range 2.5-20µm.

Physical effects in IR-coating materials

The effects of dispersion, angle of illumination and temperature in coated layers of infrared semiconductors (the IV-VI) and semiinsulators (the II-VI) are described. Examples are given of microcomputer calculations of these.

New half-sandwich heterobimetallic CpMPt (M=Rh, Ir) dithiolato bridged complexes

Cationic heterobimetallic complexes 5–7 [(PPh3)2Pt(μ-edt)MClCp′)]BF4 (edt=−S(CH2)2S−; 5: M=Rh and Cp′=η5-C5H5; 6: M=Rh and Cp′=η5-C5Me5 and 7: M=Ir and Cp′=η5-C5Me5) were prepared by reaction of [Pt(edt)(PPh3)2] with [Cp′ClM(μ-Cl)2MClCp′] in THF in the presence of two equivalents of AgBF4. The crystalline structure of 5 was determined by X-ray diffraction methods. Cationic heterobimetallic complexes [(PPh3)2Pt(μ-S(CH2)2S)MClCp′)]BF4 (M=Rh, Ir) were prepared. The crystalline structure of [(PPh3)2Pt(μ-edt)RhClCp)]BF4 was determined by X-ray diffraction methods.

A comparison among four different retrieval methods for ice-cloud properties using data from CloudSat, CALIPSO, and MODIS

The A-Train constellation of satellites provides a new capability to measure vertical cloud profiles that leads to more detailed information on ice-cloud microphysical properties than has been possible up to now. A variational radar–lidar ice-cloud retrieval algorithm (VarCloud) takes advantage of the complementary nature of the CloudSat radar and Cloud–Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) lidar to provide a seamless retrieval of ice water content, effective radius, and extinction coefficient from the thinnest cirrus (seen only by the lidar) to the thickest ice cloud (penetrated only by the radar). In this paper, several versions of the VarCloud retrieval are compared with the CloudSat standard ice-only retrieval of ice water content, two empirical formulas that derive ice water content from radar reflectivity and temperature, and retrievals of vertically integrated properties from the Moderate Resolution Imaging Spectroradiometer (MODIS) radiometer. The retrieved variables typically agree to within a factor of 2, on average, and most of the differences can be explained by the different microphysical assumptions. For example, the ice water content comparison illustrates the sensitivity of the retrievals to assumed ice particle shape. If ice particles are modeled as oblate spheroids rather than spheres for radar scattering then the retrieved ice water content is reduced by on average 50% in clouds with a reflectivity factor larger than 0 dBZ. VarCloud retrieves optical depths that are on average a factor-of-2 lower than those from MODIS, which can be explained by the different assumptions on particle mass and area; if VarCloud mimics the MODIS assumptions then better agreement is found in effective radius and optical depth is overestimated. MODIS predicts the mean vertically integrated ice water content to be around a factor-of-3 lower than that from VarCloud for the same retrievals, however, because the MODIS algorithm assumes that its retrieved effective radius (which is mostly representative of cloud top) is constant throughout the depth of the cloud. These comparisons highlight the need to refine microphysical assumptions in all retrieval algorithms and also for future studies to compare not only the mean values but also the full probability density function.

An assessment of the MODIS collection 5 leaf area index product for a region of mixed coniferous forest

Canopy leaf area index (LAI), defined as the single-sided leaf area per unit ground area, is a quantitative measure of canopy foliar area. LAI is a controlling biophysical property of vegetation function, and quantifying LAI is thus vital for understanding energy, carbon and water fluxes between the land surface and the atmosphere. LAI is routinely available from Earth Observation (EO) instruments such as MODIS. However EO-derived estimates of LAI require validation before they are utilised by the ecosystem modelling community. Previous validation work on the MODIS collection 4 (c4) product suggested considerable error especially in forested biomes, and as a result significant modification of the MODIS LAI algorithm has been made for the most recent collection 5 (c5). As a result of these changes the current MODIS LAI product has not been widely validated. We present a validation of the MODIS c5 LAI product over a 121 km2 area of mixed coniferous forest in Oregon, USA, based on detailed ground measurements which we have upscaled using high resolution EO data. Our analysis suggests that c5 shows a much more realistic temporal LAI dynamic over c4 values for the site we examined. We find improved spatial consistency between the MODIS c5 LAI product and upscaled in situ measurements. However results also suggest that the c5 LAI product underestimates the upper range of upscaled in situ LAI measurements.

Comparison of MODIS broadband albedo over an agricultural site with ground measurements and values derived from Earth observation data at a range of spatial scales

Land surface albedo is dependent on atmospheric state and hence is difficult to validate. Over the UK persistent cloud cover and land cover heterogeneity at moderate (km-scale) spatial resolution can also complicate comparison of field-measured albedo with that derived from instruments such as the Moderate Resolution Imaging Spectrometer (MODIS). A practical method of comparing moderate resolution satellite-derived albedo with ground-based measurements over an agricultural site in the UK is presented. Point measurements of albedo made on the ground are scaled up to the MODIS resolution (1 km) through reflectance data obtained at a range of spatial scales. The point measurements of albedo agreed in magnitude with MODIS values over the test site to within a few per cent, despite problems such as persistent cloud cover and the difficulties of comparing measurements made during different years. Albedo values derived from airborne and field-measured data were generally lower than the corresponding satellite-derived values. This is thought to be due to assumptions made regarding the ratio of direct to diffuse illumination used when calculating albedo from reflectance. Measurements of albedo calculated for specific times fitted closely to the trajectories of temporal albedo derived from both Systeme pour l'Observation de la Terre (SPOT) Vegetation (VGT) and MODIS instruments.

A Habermasian model of stakeholder (non)engagement and corporate (ir)responsibility reporting

Inspired by Habermas’ works, we develop a prescriptive conceptual model of stakeholder engagement and corporate social responsibility (CSR) reporting against which empirical descriptions can be compared and contrasted. We compare the high profile case of Kraft's takeover of Cadbury with the conceptual model to illustrate the gap between an ideal speech situation and practice. The paper conducts a desk study of documents relating to the takeover and interviews with stakeholders from the local community to gauge their views of stakeholder engagement and CSR reporting by Cadbury/Kraft. The findings lead to policy recommendations for enhancing stakeholder accountability through improved steering mechanisms.

Multiscale geostatistical analysis of AVHRR, SPOT-VGT, and MODIS global NDVI products

Global NDVI data are routinely derived from the AVHRR, SPOT-VGT, and MODIS/Terra earth observation records for a range of applications from terrestrial vegetation monitoring to climate change modeling. This has led to a substantial interest in the harmonization of multisensor records. Most evaluations of the internal consistency and continuity of global multisensor NDVI products have focused on time-series harmonization in the spectral domain, often neglecting the spatial domain. We fill this void by applying variogram modeling (a) to evaluate the differences in spatial variability between 8-km AVHRR, 1-km SPOT-VGT, and 1-km, 500-m, and 250-m MODIS NDVI products over eight EOS (Earth Observing System) validation sites, and (b) to characterize the decay of spatial variability as a function of pixel size (i.e. data regularization) for spatially aggregated Landsat ETM+ NDVI products and a real multisensor dataset. First, we demonstrate that the conjunctive analysis of two variogram properties – the sill and the mean length scale metric – provides a robust assessment of the differences in spatial variability between multiscale NDVI products that are due to spatial (nominal pixel size, point spread function, and view angle) and non-spatial (sensor calibration, cloud clearing, atmospheric corrections, and length of multi-day compositing period) factors. Next, we show that as the nominal pixel size increases, the decay of spatial information content follows a logarithmic relationship with stronger fit value for the spatially aggregated NDVI products (R2 = 0.9321) than for the native-resolution AVHRR, SPOT-VGT, and MODIS NDVI products (R2 = 0.5064). This relationship serves as a reference for evaluation of the differences in spatial variability and length scales in multiscale datasets at native or aggregated spatial resolutions. The outcomes of this study suggest that multisensor NDVI records cannot be integrated into a long-term data record without proper consideration of all factors affecting their spatial consistency. Hence, we propose an approach for selecting the spatial resolution, at which differences in spatial variability between NDVI products from multiple sensors are minimized. This approach provides practical guidance for the harmonization of long-term multisensor datasets.

Using paint to investigate fires: an ATR-IR study of the degradation of paint samples upon heating

Fire investigation is a challenging area for the forensic investigator. The aim of this work was to use spectral changes to paint samples to estimate the temperatures to which a paint has been heated. Five paint samples (one clay paint, two car paints, one metallic paint, and one matt emulsion) have been fully characterized by a combination of attenuated total reflectance Fourier transform infrared (ATR-IR), Raman, X-ray fluorescence spectroscopy and powder X-ray diffraction. The thermal decomposition of these paints has been investigated by means of ATR-IR and thermal gravimetric analysis. Clear temperature markers are observed in the ATR-IR spectra namely: loss of m(C = O) band, >300°C; appearance of water bands on cooling, >500°C; alterations to m(Si–O) bands due to dehydration of silicate clays, >700°C; diminution of m(CO3) and d(CO3) modes of CaCO3, >950°C. We suggest the possible use of portable ATR-IR for nondestructive, in situ analysis of paints.

Low cost, patterning of human hNT brain cells on parylene-C with UV & IR laser machining

This paper describes the use of 800nm femtosecond infrared (IR) and 248nm nanosecond ultraviolet (UV) laser radiation in performing ablative micromachining of parylene-C on SiO2 substrates for the patterning of human hNT astrocytes. Results are presented that support the validity of using IR laser ablative micromachining for patterning human hNT astrocytes cells while UV laser radiation produces photo-oxidation of the parylene-C and destroys cell patterning. The findings demonstrate how IR laser ablative micromachining of parylene-C on SiO2 substrates can offer a low cost, accessible alternative for rapid prototyping, high yield cell patterning.

A synchrotron powder X-ray diffraction study of the skutterudite-related phases AB1.5Te1.5 (A=Co, Rh, Ir; B= Ge, Sn)

X-ray resonant scattering has been exploited to investigate the crystal structure of the AB1.5Te1.5 phases (A = Co, Rh, Ir; B = Ge, Sn). Analysis of the diffraction data reveals that CoGe1.5Te1.5 and ASn1.5Te1.5 adopt a rhombohedral skutterudite-related structure, containing diamond-shape B2Te2 rings, in which the B and Te atoms are ordered and trans to each other. Anion ordering is however incomplete, and with increasing the size of both cations and anions, the degree of anion ordering decreases. By contrast, the diffraction data of IrGe1.5Te1.5 are consistent with an almost statistical distribution of the anions over the available sites, although some ordered domains may be present. The thermoelectric properties of these materials are discussed in the light of these results.