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At least 127 records · Page 7

Investigating vibrational relaxation in cyanide-bridged transition metal mixed-valence complexes using two-dimensional infrared and infrared pump-probe spectroscopies

Using polarization-selective two-dimensional infrared (2D IR) and infrared pumpprobe spectroscopies, we study vibrational relaxation of the four cyanide stretching (CN) vibrations found in [(NH3)5RuIIINCFeII(CN)5] (FeRu) dissolved in D2O or formamide and [(NC)5FeIICNPtIV(NH3)4NCFeII(CN)5] 4 (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as models for understanding the role high frequency vibrational modes play in metal-to-metal charge transfers over a bridging ligand. However, there is currently little information about vibrational relaxation and dephasing dynamics of the anharmonically coupled CN modes in the electronic ground state of these complexes. IR pump-probe experiments reveal that the vibrational lifetimes of the CN modes are 2 times faster when FeRu is dissolved in D2O versus formamide. They also reveal that the vibrational lifetimes of the CN modes of FePtFe in D2O are almost four times as long as for FeRu in D2O. Combined with mode-specific relaxation dynamics measured from the 2D IR experiments, the IR pump-probe experiments also reveal that intramolecular vibrational relaxation is occurring in all three systems on 1 ps timescale. Center line slope dynamics, which have been shown to be a measure of the frequency-frequency correlation function, reveal that the radial, axial, and trans CN modes exhibit a 3 ps timescale for frequency fluctuations. This timescale is attributed to the forming and breaking of hydrogen bonds between each mode and the solvent. The results presented here along with our previous work on FeRu and FePtFe reveal a picture of coupled anharmonic CN modes where the spectral diffusion and vibrational relaxation dynamics depend on the spatial localization of the mode on the molecular complex and its specific interaction with the solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultra low emittance electron beams from multi-alkali antimonide photocathode operated with infrared light

The intrinsic emittance of electron beams generated from a multi-alkali photocathode operated in a high voltage DC gun is reported. The photocathode showed sensitivity extending to the infrared part of the spectrum up to 830 nm. The measured intrinsic emittances of electron beams generated with light having wavelength longer than 800 nm are approaching the limit imposed by the thermal energy of electrons at room temperature with quantum efficiencies comparable to metallic photocathodes used in operation of modern photoinjectors.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Two-center three-electron bonding in ClNH{sub 3} revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH{sub 3} → ClNH{sub 2} + H reaction

Pyrolytic dissociation of Cl{sub 2} is employed to dope helium droplets with single Cl atoms. Sequential addition of NH{sub 3} to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH{sub 3} → ClNH{sub 2} + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C{sub 3v} symmetric top. Frequency shifts from NH{sub 3} and dipole moment measurements are consistent with a ClNH{sub 3} complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH{sub 3} is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH{sub 3}Cl and Cl–HNH{sub 2}, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH{sub 3} → HCl + NH{sub 2}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design and characterization of a prototype divertor viewing infrared video bolometer for NSTX-U

The InfraRed Video Bolometer (IRVB) is a powerful tool to measure radiated power in magnetically confined plasmas due to its ability to obtain 2D images of plasma emission using a technique that is compatible with the fusion nuclear environment. A prototype IRVB has been developed and installed on NSTX-U to view the lower divertor. The IRVB is a pinhole camera which images radiation from the plasma onto a 2.5 μm thick, 9 × 7 cm{sup 2} Pt foil and monitors the resulting spatio-temporal temperature evolution using an IR camera. The power flux incident on the foil is calculated by solving the 2D+time heat diffusion equation, using the foil’s calibrated thermal properties. An optimized, high frame rate IRVB, is quantitatively compared to results from a resistive bolometer on the bench using a modulated 405 nm laser beam with variable power density and square wave modulation from 0.2 Hz to 250 Hz. The design of the NSTX-U system and benchtop characterization are presented where signal-to-noise ratios are assessed using three different IR cameras: FLIR A655sc, FLIR A6751sc, and SBF-161. The sensitivity of the IRVB equipped with the SBF-161 camera is found to be high enough to measure radiation features in the NSTX-U lower divertor as estimated using SOLPS modeling. The optimized IRVB has a frame rate up to 50 Hz, high enough to distinguish radiation during edge-localized-modes (ELMs) from that between ELMs.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Far-infrared tangential interferometer/polarimeter design and installation for NSTX-U

The Far-infrared Tangential Interferometer/Polarimeter (FIReTIP) system has been refurbished and is being reinstalled on the National Spherical Torus Experiment—Upgrade (NSTX-U) to supply real-time line-integrated core electron density measurements for use in the NSTX-U plasma control system (PCS) to facilitate real-time density feedback control of the NSTX-U plasma. Inclusion of a visible light heterodyne interferometer in the FIReTIP system allows for real-time vibration compensation due to movement of an internally mounted retroreflector and the FIReTIP front-end optics. Real-time signal correction is achieved through use of a National Instruments CompactRIO field-programmable gate array.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Massive young stellar object W42-MME: The discovery of an infrared jet using VLT/NACO near-infrared images

We report on the discovery of an infrared jet from a deeply embedded infrared counterpart of the 6.7 GHz methanol maser emission (MME) in W42 (i.e., W42-MME). We show that W42-MME drives a parsec-scale H{sub 2} outflow, with the detection of a bow shock feature at ∼0.52 pc to the north. The inner ∼0.4 pc part of the H{sub 2} outflow has a position angle of ∼18° and the position angle of ∼40° is found farther away on either side of the outflow from W42-MME. W42-MME is detected at wavelengths longer than 2.2 μm and is a massive young stellar object with an estimated stellar mass of 19 ± 4 M{sub ⊙}. We map the inner circumstellar environment of W42-MME using Very Large Telescope (VLT)/NACO adaptive optics K{sub s} and L′ observations at resolutions of ∼0.″ 2 and ∼0.″1, respectively. We discover a collimated jet in the inner 4500 AU using the L′ band, which contains prominent Brα line emission. The jet is located inside an envelope/cavity (extent ∼10,640 AU) that is tapered at both ends and is oriented along the north–south direction. Such observed morphology of the outflow cavity around the massive star is scarcely known and is very crucial for understanding the jet-outflow formation process in massive star formation. Along the flow axis, which is parallel to the previously known magnetic field, two blobs are found in both the NACO images at distances of ∼11800 AU, located symmetrically from W42-MME. The observed W42-MME jet-outflow configuration can be used to constrain the jet launching and jet collimation models in massive star formation.

79 ASTRONOMY AND ASTROPHYSICS↗

Infrared studies of gas phase and surface processes of the enhancement of catalytic methane decomposition by low temperature plasma

Catalyst enhancement by atmospheric pressure plasma is a recently emerging field of research that embodies a complex system of reactive species and how they interact with surfaces. In this work we use an atmospheric pressure plasma jet integrated with a nickel on Al 2 O 3 /SiO 2 support catalyst material to decompose methane gas by partial oxidation reaction. We use Fourier-transform Infrared spectroscopy (FTIR) analysis of the gas phase post reaction to measure the loss of methane and the production of CO, CO 2 , and H 2 O and diffuse reflectance Fourier-transform Infrared spectroscopy (DRIFTs) in situ analysis of the catalyst surface as a function of both catalyst temperature and plasma operating parameters. We find reduction of methane by both plasma alone, catalyst alone, and an increase when both plasma and catalyst were simultaneously used. The production of CO appears to be due primarily to the plasma source as it only appears above 2.5 W plasma dissipated power and decreases as catalyst temperature increases. CO 2 production is enhanced by having the catalyst at high temperature and H 2 O production depends on both plasma power and temperature. Using DRIFTs we find that both heating and plasma treatment remove absorbed water on the surface of the catalyst. Plasma treatment alone however leads to the formation of CO and another IR spectral feature at 1590 cm -1 , which may be attributed to carboxylate groups, bonded to the catalyst surface. These species exhibit a regime of plasma treatment where they are formed on the surface and where they are significantly removed from the catalyst surface. We see the formation of a new spectral feature at 995 cm -1 and discuss the behavior and possible origins of this feature. Furthermore, this research highlights the potential for plasma regeneration of catalyst materials as well as showing enhancement of the catalytic behavior under low temperature plasma treatment.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Combining Dark Energy Survey Science Verification data with near-infrared data from the ESO VISTA Hemisphere Survey

We present the combination of optical data from the Science Verification phase of the Dark Energy Survey (DES) with near-infrared (NIR) data from the European Southern Observatory VISTA Hemisphere Survey (VHS). The deep optical detections from DES are used to extract fluxes and associated errors from the shallower VHS data. Joint seven-band ( grizYJK ) photometric catalogues are produced in a single 3 sq-deg dedicated camera field centred at 02h26m-04d36m where the availability of ancillary multiwavelength photometry and spectroscopy allows us to test the data quality. Dual photometry increases the number of DES galaxies with measured VHS fluxes by a factor of ~4.5 relative to a simple catalogue level matching and results in a ~1.5 mag increase in the 80 per cent completeness limit of the NIR data. Almost 70 per cent of DES sources have useful NIR flux measurements in this initial catalogue. Photometric redshifts are estimated for a subset of galaxies with spectroscopic redshifts and initial results, although currently limited by small number statistics, indicate that the VHS data can help reduce the photometric redshift scatter at both z < 0.5 and z > 1. We present example DES+VHS colour selection criteria for high-redshift luminous red galaxies (LRGs) at z ~ 0.7 as well as luminous quasars. Using spectroscopic observations in this field we show that the additional VHS fluxes enable a cleaner selection of both populations with <10 per cent contamination from galactic stars in the case of spectroscopically confirmed quasars and <0.5 per cent contamination from galactic stars in the case of spectroscopically confirmed LRGs. The combined DES+VHS data set, which will eventually cover almost 5000 sq-deg, will therefore enable a range of new science and be ideally suited for target selection for future wide-field spectroscopic surveys.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Near-infrared noise in intense electron bunches

This article investigates electron bunch density fluctuations in the 1 −10 μ⁢m wavelength range, focusing on their impact on coherent electron cooling (CEC) in hadron storage rings. In this study, we compare the shot-noise model with experimental observations using bandwidth-filtered near-infrared optical transition radiation (OTR) photodiode signals, where the transverse bunch size is much larger than the OTR wavelength of interest. The relativistic electron bunch (𝛾 ≈ 50) parameters are close to those proposed for the coherent electron cooler in the electron-ion collider (EIC) project. Preliminary feasibility experiments were conducted, and the noise factors are presented, supported by particle tracking. No major density fluctuations or effective cooling rate decrease were revealed for EIC CEC design parameters. Additionally, longitudinal-space-charge-induced microbunching for the chicane-compressed bunch was observed with coherent OTR enhancements up to 100 times, providing further calibration of the measurement method.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Infrared divergences in QED revisited

Recently it has been demonstrated that the vacuum state in QED is infinitely degenerate. Moreover a transition among the degenerate vacua is induced in any nontrivial scattering process and determined from the associated soft factor. Conventional computations of scattering amplitudes in QED do not account for this vacuum degeneracy and therefore always give zero. This vanishing of all conventional QED amplitudes is usually attributed to infrared divergences. In this work, we show that if these vacuum transitions are properly accounted for, the resulting amplitudes are nonzero and infrared finite. Our construction of finite amplitudes is mathematically equivalent to, and amounts to a physical reinterpretation of, the 1970 construction of Faddeev and Kulish.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Infrared absorption cross section of SiN x thin films

At the molecular level, resonant coupling of infrared radiation with oscillations of the electric dipole moment determines the absorption cross section, $σ$. The parameter σ relates the bond density to the total integrated absorption. In this work, $σ$ was measured for the Si–N asymmetric stretch mode in SiN x thin films of varying composition and thickness. Thin films were deposited by low pressure chemical vapor deposition at 850 °C from mixtures of dichlorosilane and ammonia. σ for each film was determined from Fourier transform infrared spectroscopy and ellipsometric measurements. Increasing the silicon content from 0% to 25% volume fraction amorphous silicon led to increased optical absorption and a corresponding systematic increase in σ from 4.77 × 10 –20 to 6.95 × 10 –20 cm 2 , which is consistent with literature values. The authors believe that this trend is related to charge transfer induced structural changes in the basal SiN x tetrahedron as the volume fraction of amorphous silicon increases. Furthermore, experimental $σ$ values were used to calculate the effective dipole oscillating charge, q, for four films of varying composition. The authors find that q increases with increasing amorphous silicon content, indicating that compositional factors contribute to modulation of the Si–N dipole moment. Additionally, in the composition range investigated, the authors found that $σ$ agrees favorably with trends observed in films deposited by plasma enhanced chemical vapor deposition.

36 MATERIALS SCIENCE↗

Non-Destructive Evaluation of Polyolefin Thermal Aging Using Infrared Spectroscopy

Fourier transform infrared (FTIR) spectroscopy is an information-rich method that reveals chemical bonding near the surface of polymer composites. FTIR can be used to verify composite composition, identify chemical contaminants and expose composite moisture content. Polymer matrix changes due to thermal exposure including loss of additives, chain scission, oxidation and changes in crystallinity may also be determined using FTIR spectra. Portable handheld instruments using non-contact reflectance or surface contact attenuated total reflectance (ATR) may be used for non-destructive evaluation (NDE) of thermal aging in polymer and composite materials of in-service components. We report the use of ATR FTIR to track oxidative thermal aging in ethylene-propylene rubber (EPR) and chlorinated polyethylene (CPE) materials used in medium voltage nuclear power plant electrical cable insulation and jacketing. Mechanical property changes of the EPR and CPE materials with thermal degradation for correlation with FTIR data are tracked using indenter modulus (IM) testing. IM is often used as a local NDE metric of cable jacket health. The FTIR-determined carbonyl index was found to increase with IM and may be a valuable NDE metric with advantages over IM for assessing cable remaining useful life.

aging↗

Longwave infrared (6.6–11.4 µm) dual-comb spectroscopy with 240,000 comb-mode-resolved data points at video rate

Using sub-3-cycle pulses from mode-locked Cr:ZnS lasers at λ ≈ 2.4 µm as a driving source, we performed high-resolution dual-frequency-comb spectroscopy in the longwave infrared (LWIR) range. A duo of highly coherent broadband (6.6–11.4 µm) frequency combs were produced via intrapulse difference frequency generation in zinc germanium phosphide (ZGP) crystals. Fast (up to 0.1 s per spectrum) acquisition of 240,000 comb-mode-resolved data points, spaced by 80 MHz and referenced to a Rb clock, was demonstrated, resulting in metrology grade molecular spectra of N 2 O (nitrous oxide) and CH 3 OH (methane). The key to high-speed massive spectral data acquisition was low intensity and phase noise of the LWIR combs and high (7.5%) downconversion efficiency, resulting in a LWIR power of 300 mW for each comb.

Vasilyev, Sergey (ORCID:0000000225203547)↗

Analysis of the Intrinsic Mid-infrared L band to Visible–Near-infrared Flux Ratios in Spectral Synthesis Models of Composite Stellar Populations

We analyze the intrinsic flux ratios of various visible–near-infrared filters with respect to 3.5 μm for simple and composite stellar populations (CSPs), and their dependence on age, metallicity, and star formation history (SFH). UV/optical light from stars is reddened and attenuated by dust, where different sightlines across a galaxy suffer varying amounts of extinction. Tamura et al. (2009) developed an approximate method to correct for dust extinction on a pixel-by-pixel basis, dubbed the “β{sub V}” method, by comparing the observed flux ratio to an empirical estimate of the intrinsic ratio of visible and ∼3.5 μm data. Through extensive modeling, we aim to validate the “β{sub V}” method for various filters spanning the visible through near-infrared wavelength range, for a wide variety of simple and CSPs. Combining Starburst99 and BC03 models, we built spectral energy distributions (SEDs) of simple (SSP) and composite (CSP) stellar populations for various realistic SFHs, while taking metallicity evolution into account. We convolve various 0.44–1.65 μm filter throughput curves with each model SED to obtain intrinsic flux ratios β{sub λ,0}. When unconstrained in redshift, the total allowed range of β{sub V,0} is 0.6–4.7, or almost a factor of eight. At known redshifts, and in particular at low redshifts (z ≲ 0.01), β{sub V,0} is predicted to span a narrow range of 0.6–1.9, especially for early-type galaxies (0.6–0.7), and is consistent with observed β{sub V} values. The β{sub λ} method can therefore serve as a first-order dust-correction method for large galaxy surveys that combine JWST (rest-frame 3.5 μm) and HST (rest-frame visible–near-IR) data.

79 ASTRONOMY AND ASTROPHYSICS↗

Infrared Emission from Kilonovae: The Case of the Nearby Short Hard Burst GRB 160821B

In this paper, we present constraints on Ks-band emission from one of the nearest short hard gamma-ray bursts, GRB 160821B, at z = 0.16, at three epochs. We detect a red relativistic afterglow from the jetted emission in the first epoch but do not detect any excess kilonova emission in the second two epochs. We compare upper limits obtained with Keck I/MOSFIRE to multi-dimensional radiative transfer models of kilonovae, that employ composition-dependent nuclear heating and LTE opacities of heavy elements. We discuss eight models that combine toroidal dynamical ejecta and two types of wind and one model with dynamical ejecta only. We also discuss simple, empirical scaling laws of predicted emission as a function of ejecta mass and ejecta velocity. Our limits for GRB 160821B constrain the ejecta mass to be lower than 0.03 M ⊙ for velocities greater than 0.1 c. At the distance sensitivity range of advanced LIGO, similar ground-based observations would be sufficiently sensitive to the full range of predicted model emission including models with only dynamical ejecta. Finally, the color evolution of these models shows that I–K color spans 7–16 mag, which suggests that even relatively shallow infrared searches for kilonovae could be as constraining as optical searches.

79 ASTRONOMY AND ASTROPHYSICS↗