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IrBr6N2 is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is zero-dimensional and consists of eight ammonia molecules and four IrBr6 clusters. In each IrBr6 cluster, Ir4+ is bonded in an octahedral geometry to six equivalent Br1- atoms. All Ir–Br bond lengths are 2.46 Å. Br1- is bonded in a single-bond geometry to one Ir4+ atom.
IrCl6N2 is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is zero-dimensional and consists of eight ammonia molecules and four IrCl6 clusters. In each IrCl6 cluster, Ir4+ is bonded in an octahedral geometry to six equivalent Cl1- atoms. All Ir–Cl bond lengths are 2.30 Å. Cl1- is bonded in a single-bond geometry to one Ir4+ atom.
Photodetectors with ultrafast response are explored using inorganic/organic hybrid perovskites. High responsivity and fast optoelectronic response are achieved due to the exceptional semiconducting properties of perovskite materials. However, most of the perovskite-based photodetectors exploited to date are centered on Pb-based perovskites, which only afford spectral response across the visible spectrum. This study demonstrates a high-performance near-IR (NIR) photodetector using a stable low-bandgap Sn-containing perovskite, (CH 3 NH 3 ) 0.5 (NH 2 CHNH 2 ) 0.5 Pb 0.5 Sn 0.5 I 3 (MA 0.5 FA 0.5 Pb 0.5 Sn 0.5 I 3 ), which is processed with an antioxidant additive, ascorbic acid (AA). The addition of AA effectively strengthens the stability of Sn-containing perovskite against oxygen, thereby significantly inhibiting the leakage current. Consequently, the derived photodetector shows high responsivity with a detectivity of over 10 12 Jones ranging from 800 to 970 nm. Such low-cost, solution processable NIR photodetectors with high performance show promising potential for future optoelectronic applications.
Epitaxial growth of graphene on transition metal crystals, such as Ru,⁽¹⁻³⁾ Ir,⁽⁴⁻⁶⁾ and Ni,⁽⁷⁾ provides large-area, uniform graphene layers with controllable defect density, which is crucial for practical applications in future devices. To decrease the high cost of single-crystalline metal bulks, single-crystalline metal films are strongly suggested as the substrates for epitaxial growth large-scale high-quality graphene.⁽⁸⁻¹⁰⁾ Moreover, in order to weaken the interactions of graphene with its metal host, which may result in a suppression of the intrinsic properties of graphene,⁽¹¹ ¹²⁾ the method of element intercalation of semiconductors at the interface between an epitaxial graphene layer and a transition metal substrate has been successfully realized.⁽¹³⁻¹⁶⁾
Access to synchrotron X-ray facilities has become an important aspect for many disciplines in experimental Earth science. This is especially important for studies that rely on probing samples in situ under natural conditions different from the ones found at the surface of the Earth. The non-ambient condition Earth science program at the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory, offers a variety of tools utilizing the infra-red and hard X-ray spectrum that allow Earth scientists to probe Earth and environmental materials at variable conditions of pressure, stress, temperature, atmospheric composition, and humidity. These facilities are important tools for the user community in that they offer not only considerable capacity (non-ambient condition diffraction) but also complementary (IR spectroscopy, microtomography), and in some cases unique (Laue microdiffraction) instruments. The availability of the ALS’ in situ probes to the Earth science community grows especially critical during the ongoing dark time of the Advanced Photon Source in Chicago, which massively reduces available in situ synchrotron user time in North America.
Although linear accelerators are used in many security, industrial and medical applications, the existing technologies are too large and expensive for several critical applications such as radioactive source replacement, field radiography and mobile cargo scanners. Here, one of the main requirements for these sources is to be highly portable to allow field operation. In response to this problem, RadiaBeam has designed a hand-portable 1 MeV X-ray source, scalable to higher energies, based on Ku-band split electron linac, that can be used for Ir-192 radioisotope replacement. In this paper, we present its multiphysics and engineering design studies, as well as an accelerating structure prototype along with RF measurements.
Accelerated aging of polymers at elevated temperatures often involves the generation of volatiles. These can be formed as the products of oxidative degradation reactions or intrinsic pyrolytic decomposition as part of polymer scission reactions. A simple analytical method for the quantification of water, CO 2 , and CO as fundamental signatures of degradation kinetics is required. Here, we describe an analytical framework and develops a rapid mid-IR based gas analysis methodology to quantify volatiles that are contained in small ampoules after aging exposures. The approach requires identification of unique spectral signatures, systematic calibration with known concentrations of volatiles, and a rapid acquisition FTIR spectrometer for time resolved successive spectra. Furthermore, the volatiles are flushed out from the ampoule with dry N2 carrier gas and are then quantified through spectral and time integration. This method is sufficiently sensitive to determine absolute yields of ~50 μg water or CO 2 , which relates to probing mass losses of less than 0.01% for a 1 g sample, i.e. the early stages in the degradation process. Such quantitative gas analysis is not easily achieved with other approaches. Our approach opens up the possibility of quantitative monitoring of volatile evolution as an avenue to explore polymer degradation kinetics and its dependence on time and temperature.
Near-IR (NIR) lumiphores are advantageous for biological applications as their emission falls within the tissue-transparent region. Furthermore, these dyes suffer from low quantum yields as a consequence of their low transition energy. Heteroatom substitution has recently been successfully used to bathochromically shift emission in various dye scaffolds while maintaining bright emission.
Hydrogen generation from formic acid (FA), one of the most promising hydrogen storage materials, has attracted much attention due to the demand for the development of renewable energy carriers. Catalytic dehydrogenation of FA in an efficient and green manner remains challenging. Here, we report a series of bio-inspired Ir complexes for highly robust and selective hydrogen production from FA in aqueous solutions without organic solvents or additives. One of these complexes bearing an imidazoline moiety (complex 6 ) achieved a turnover frequency (TOF) of 322,000 h⁻¹ at 100 °C, which is higher than ever reported. The novel catalysts are very stable and applicable in highly concentrated FA. For instance, complex 3 (1 μmol) affords an unprecedented turnover number (TON) of 2,050,000 at 60 °C. Deuterium kinetic isotope effect experiments and density functional theory (DFT) calculations employing a “speciation” approach demonstrated a change in the rate-determining step with increasing solution pH. This study provides not only more insight into the mechanism of dehydrogenation of FA but also offers a new principle for the design of effective homogeneous organometallic catalysts for H₂ generation from FA.
Glycolaldehyde (GA, 2-hydroxyethanal, C2H4O2) is a semi-volatile molecule of atmospheric importance, recently proposed as a precursor in the formation of aqueous-phase secondary organic aerosol (SOA). There are few methods to measure glycolaldehyde vapor, but infrared spectroscopy has been used successfully. Using vetted protocols we have completed the first assignment of all fundamental vibrational modes and derived quantitative IR absorption band strengths using both neat and pressure-broadened GA vapor. Even though GA is problematic due to its propensity to both dimerize and condense, our intensities agree well with the few previously published values. Using the reference ν10 band Q-branch at 860.51 cm-1, we have also determined GA mixing ratios in biomass burning plumes generated by field and laboratory burns of fuels from the southeastern and southwestern United States, including the first field measurements of glycolaldehyde in smoke. The GA emission factors were anti-correlated with modified combustion efficiency confirming release of GA from smoldering combustion. The GA emission factors (g of GA emitted per kg dry biomass burned on a dry mass basis) had a low dependence on fuel type consistent with the production mechanism being pyrolysis of cellulose. GA was emitted at 0.23 ± 0.13% of CO from field fires and we calculate that it accounts for ~18% of the aqueous-phase SOA precursors that we were able to measure.
Significance Self-assembled monolayers (SAMs) are a form of nanotechnology that enables the functionalization of surfaces with single layers of chemically designed structures having tuned properties. In contrast to the characterization of time-average static structures, it is challenging to measure the dynamic behavior of SAMs on the timescales of molecular motions, i.e. picoseconds. Here we combine 2D IR spectroscopy and molecular dynamics (MD) simulations to investigate alkyl chain monolayers functionalized with a head group. The dynamics reported by the head group are induced by the alkyl chain motions. For example, it was determined that SAMs with higher alkyl chain gauche defect content have faster dynamics caused by more frequent chain conformational fluctuations.
Fast near-IR (NIR) emitters are highly valuable in telecommunications and biological imaging. The most established NIR emitters are epitaxially grown In x Ga 1-x As quantum dots (QDs), but epitaxial growth has several disadvantages. Colloidal synthesis is a viable alternative that produces a few NIR-emitting materials, but they suffer from long photoluminescence (PL) times. These long PL times are intrinsic in some NIR materials (PbS, PbSe) but are attributed to emission from bright trapped carrier states in others. We show that Cd 3 P 2 QDs possess substantial trap emission with radiative times >10 1 ns. Surface passivation through shell growth or coordination of Lewis acids is shown to accelerate the NIR emission from Cd 3 P 2 QDs by decreasing the amount of trap emission. This finding brings us one step closer to the application of colloidally synthesized QDs as quantum emitters.
The development of mid-IR semiconductor diode lasers based on type-II interband cascade structures is presented. How these diode lasers can be developed to meet the requirements in chemical sensing applications is discussed.
Comet C/2012 S1 (ISON) was unique in that it was a dynamically new comet derived from the nearly isotropic Oort cloud reservoir of comets with a sun-grazing orbit. Infrared (IR) observations were executed on NASA's Stratospheric Observatory For Infrared Astronomy (SOFIA) by the FORCAST instrument on 2013 October 25 UT (r(sub h)=1.18 AU, Delta=1.5AU). Photometry was obtained in FORCAST filters centered at 11.1, 19.7, and 31.5 micron. The observations compliment a large world-wide effort to observe and characterize comet ISON.
We have built surface micromachined thin-film metallized Si(x)N(y) optical absorbers for transition-edge sensors (TESs) suitable for the Background - Limited far-IR/Submm Spectrograph (BLISS). BLISS is a broadband (38 micrometers - 433 micrometers), grating spectrometer consisting of five wavebands each with a modest resolution of R (is) approx. 1000. Because BLISS requires the effective noise equivalent power (NEP) of the TES to be below 10 (exp 19) W/Hz(exp 1/2), our TESs consist of four long (1000 micrometers), narrow (0.4 micrometers ), and thin (0.25 micrometers ) Si(x) N(y) support beams that reduce the thermal conductance G between the substrate and the optical absorber. To reduce the heat capacity of the absorber and make the response time tau fast enough for BLISS, our absorbers are patterned into a mesh geometry with a fill factor of less than 10%. We use a bilayer of Ti/Au to make the effective impedance of the absorber match the impedance of the incoming radiation for each band. Measurements of the response time of the metallized absorbers to heat pulses show that their heat capacity exceeds the predictions of the Debye model. Our results are suggestive that the surface of the low pressure chemical vapor deposition (LPCVD) Si(x)N(y) used in the absorbers' construction is the source of microstates that dominate the heat capacity.
Developments in IRS (Implicit Rotating Source) multi-mode waveforms modeling.
Here we present our recent studies of proton-irradiated and unirradiated ammonium hydrosulfide, NH4SH, a compound predicted to be an important tropospheric cloud component of Jupiter and other giant planets. We irradiated both crystalline and amorphous NH4SH at 10-160 K and used IR spectroscopy to observe and identify reaction products in the ice, specifically NH3 and long-chained sulfur-containing ions. Crystalline NH4SH was amorphized during irradiation at all temperatures studied with the rate being the fastest at the lowest temperatures. Irradiation of amorphous NH4SH at approximately 10-75 K showed that 60-80% of the NH4 + remained when equilibrium was reached, and that NH4SH destruction rates were relatively constant within this temperature range. Irradiations at higher temperatures produced different dose dependence and were accompanied by pressure outbursts that, in some cases, fractured the ice. The thermal stability of irradiated NH4SH was found to be greater than that of unirradiated NH4SH, suggesting that an irradiated giant-planet cloud precipitate can exist at temperatures and altitudes not previously considered.
Mid-infrared spectra of amorphous and crystalline acetone are presented along with measurements of the refractive index and density for both forms of the compound. Infrared band strengths are reported for the first time for amorphous and crystalline acetone, along with IR optical constants. Vapor pressures and a sublimation enthalpy for crystalline acetone also are reported. Positions of 13C-labeled acetone are measured. Band strengths are compared to gas-phase values and to the results of a density-functional calculation. A 73% error in previous work is identified and corrected.