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At least 1,189 records · Page 66

Primary photodissociation mechanisms of pyruvic acid on S 1 : observation of methylhydroxycarbene and its chemical reaction in the gas phase

Pyruvic acid, a representative alpha-keto carboxylic acid, is one of the few organic molecules destroyed in the troposphere by solar radiation rather than by reactions with free radicals. To date, only its stable final products were identified, often with contribution from secondary chemistry, making it difficult to elucidate photodissociation mechanisms following excitation to the lowest singlet excited-state (S 1 ) and the role of the internal hydrogen bond in the most-stable Tc conformer. Using multiplexed photoionization mass spectrometry we report the first direct experimental evidence, via the observation of singlet methylhydroxycarbene (MHC) following 351 nm excitation, supporting the decarboxylation mechanism previously proposed. Decarboxylation to MHC + CO 2 represents 97–100% of product branching at 351 nm. We observe vinyl alcohol and acetaldehyde, which we attribute to isomerization of MHC. We also observe a 3 ± 2% yield of the Norrish Type I photoproducts CH 3 CO + DOCO, but only from d 1 -pyruvic acid. At 4 Torr pressure, we measure a photodissociation quantum yield of $1.0^{+0}_{–0.4}$, consistent with IUPAC recommendations. However, our measured product branching fractions disagree with IUPAC. In light of previous calculations, these results support a mechanism in which hydrogen transfer on the S 1 excited state occurs at least partially by tunneling, in competition with intersystem crossing to the T 1 state. Here, we present the first evidence of a bimolecular reaction of MHC in the gas phase, where MHC reacts with pyruvic acid to produce a C 4 H 8 O 2 product. This observation implies that some MHC produced from pyruvic acid in Earth's troposphere will be stabilized and participate in chemical reactions with O 2 and H 2 O, and should be considered in atmospheric modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selectively accessing the hotspots of optical nanoantennas by self-aligned dry laser ablation

Plasmonic nanostructures serve as optical antennas for concentrating the energy of incoming light in localized hotspots close to their surface. By positioning nanoemitters in the antenna hotspots, energy transfer is enabled, leading to novel hybrid antenna-emitter-systems, where the antenna can be used to manipulate the optical properties of the nano-objects. The challenge remains how to precisely position emitters within the hotspots. We report a self-aligned process based on dry laser ablation of a calixarene that enables the attachment of molecules within the electromagnetic hotspots at the tips of gold nanocones. Within the laser focus, the ablation threshold is exceeded in nanoscale volumes, leading to selective access of the hotspot areas. A first indication of the site-selective functionalization process is given by attaching fluorescently labelled proteins to the nanocones. In a second example, Raman-active molecules are selectively attached only to nanocones that were previously exposed in the laser focus, which is verified by surface enhanced Raman spectroscopy. Enabling selective functionalization is an important prerequisite e.g. for preparing single photon sources for quantum optical technologies, or multiplexed Raman sensing platforms.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Time-resolved quantification of key species and mechanistic insights in low-temperature tetrahydrofuran oxidation

Here, we investigate the kinetics and report the time-resolved concentrations of key chemical species in the oxidation of tetrahydrofuran (THF) at 7500 torr and 450–675 K. Experiments are carried out using high-pressure multiplexed photoionization mass spectrometry (MPIMS) combined with tunable vacuum ultraviolet radiation from the Berkely Lab Advanced Light Source. Intermediates and products are quantified using reference photoionization (PI) cross sections, when available, and constrained by a global carbon balance tracking approach at all experimental temperatures simultaneously for the species without reference cross sections. From carbon balancing, we determine time-resolved concentrations for the ROO˙ and ˙OOQOOH radical intermediates, butanedial, and the combined concentration of ketohydroperoxide (KHP) and unsaturated hydroperoxide (UHP) products stemming from the ˙QOOH + O 2 reaction. Furthermore, we quantify a product that we tentatively assign as fumaraldehyde, which arises from UHP decomposition via H 2 O or ˙OH + H loss. The experimentally derived species concentrations are compared with model predictions using the most recent literature THF oxidation mechanism of Fenard et al., (Combust. Flame, 2018, 191, 252–269). Our results indicate that the literature mechanism significantly overestimates THF consumption and the UHP + KHP concentration at our conditions. The model predictions are sensitive to the rate coefficient for the ROO˙ isomerization to ˙QOOH, which is the gateway for radical chain propagating and branching pathways. Comparisons with our recent results for cyclopentane (Demireva et al., Combust. Flame, 2023, 257, 112506) provide insights into the effect of the ether group on reactivity and highlight the need to determine accurate rate coefficients of ROO˙ isomerization and subsequent reactions.

Demireva, Maria↗

Elimination of ghosting artifacts from wavelength-shifting fiber neutron detectors

Misassignment of neutron position (ghosting) produces artifacts, which have been observed in wavelength-shifting (WLS) fiber detectors developed for time-of-flight (TOF) neutron powder diffraction. In position-sensitive detectors (PSDs) with WLS fiber encoding, thermal and cold neutrons interact with a monolithic 6LiF/ZnS:Ag scintillator screen, and scintillation photons are generated and transported through the crossed fibers to photomultipliers (PMTs). The neutron position is determined by photon counts in PMTs within a preset time window. Ghosting occurs when neutrons hit the group boundaries of two neighboring PMTs for x-position multiplexing, which is modeled as resulting from a long travel length (about 3-5 mm) of a small number of scintillation photons. This model is supported by the change observed in aperture images when the threshold number for photon-pulses was adjusted for a neutron event determination. When the threshold number of photon-pulses was set above 10 for each PMT, the ghost peaks in the aperture images and TOF spectra of powder diffraction were strongly suppressed or completely eliminated, and the intrinsic background levels of the WLS detectors were significantly reduced. Our result indicates that WLS fiber detector is a promising alternative for 3He PSDs for neutron scattering.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Solid-state framing camera with multiple time frames

A high speed solid-state framing camera has been developed which can operate over a wide range of photon energies. This camera measures the two-dimensional spatial profile of the flux incident on a cadmium selenide semiconductor at multiple times. This multi-frame camera has been tested at 3.1 eV and 4.5 keV. The framing camera currently records two frames with a temporal separation between the frames of 5 ps but this separation can be varied between hundreds of femtoseconds up to nanoseconds and the number of frames can be increased by angularly multiplexing the probe beam onto the cadmium selenide semiconductor.

36 MATERIALS SCIENCE↗

Merged vector gratings recorded in a photocrosslinkable polymer liquid crystal film for polarimetry

A merged vector grating, which is holographically fabricated in an anisotropic medium by irradiation with interference light with intensity modulation and polarization modulation, was designed to detect the polarization of light. The merged vector grating is recorded by the interference of two elliptically polarized beams with equal intensities, parallel azimuths, equal ellipticities, and different directions of rotation. We clarified theoretically that the Stokes parameters of the incident light beam are described by the diffraction efficiency of the merged vector grating. Also, to apply this property to formation of a polarimeter without any moving parts or mechanisms, two merged vector gratings with different grating vectors were recorded in a photocrosslinkable polymer liquid crystal film by angle-multiplexed holography. By investigation of the diffraction properties of the gratings obtained, we demonstrated the applicability of the merged vector gratings for use in polarimetry.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Automated inspection of surface breaking cracks using GMR sensor arrays

We present a prototype for automated magnetic stray field testing of ferromagnetic roller bearings. For this purpose NDE-adapted GMR sensor arrays (giant magneto resistance) are used for the detection of surface breaking cracks. The sensors are miniaturized down to the lower μm-regime to achieve adequate spatial resolution. In doing so, sensor arrays with up to 48 elements are used to inspect the bearing surface within a few seconds only. In contrast to magnetic particle inspection (MPI), where the global magnetization requires a further inspection step and succeeding demagnetization, the presented prototype only locally magnetize the surface area in the vicinity of the GMR Sensors. For the local magnetization, the applied sub-surface magnetic field was simulated and proofed for detecting flaws with a depth of a few 10 μm. By multiplexing the sensor array with an adapted read out electronics we quasi simultaneously detect the normal field component of about 100μm above the surface. The detection of artificial notches with a depth of 40 μm and more could be resolved with a SNR better than 20 dB. The presented testing facility is fast and provides a step towards automated testing of safety relevant steel components.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

In-situ weak-beam and polarization control of multidimensional laser sidebands for ultrafast optical switching

All-optical switching has myriad applications in optoelectronics, optical communications, and quantum information technology. To achieve ultrafast optical switching in a compact yet versatile setup, we demonstrate distinct sets of two-dimensional (2D) broadband up-converted multicolor arrays (BUMAs) in a thin type-I β-barium-borate crystal with two noncollinear near-IR femtosecond pulses at various phase-matching conditions. The unique interaction mechanism is revealed as quadratic spatial solitons (QSSs)-coupled cascaded four-wave mixing (CFWM), corroborated by numerical calculations of the governing phase-matching conditions. Broad and continuous spectral-spatial tunability of the 2D BUMAs are achieved by varying the time delay between the two incident pulses that undergo CFWM interaction, rooted in the chirped nature of the weak white light and the QSSs generation of the intense fundamental beam. The control of 2D BUMAs is accomplished via seeding a weak second-harmonic pulse in situ to suppress the 2D arrays with polarization dependence on the femtosecond timescale that matches the control pulse duration of ∼35 fs. A potential application is proposed on femtosecond all-optical switching in an integrated wavelength-time division multiplexing device.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A spatially resolved retarding field energy analyzer design suitable for uniformity analysis across the surface of a semiconductor wafer

A novel retarding field energy analyzer design capable of measuring the spatial uniformity of the ion energy and ion flux across the surface of a semiconductor wafer is presented. The design consists of 13 individual, compact-sized, analyzers, all of which are multiplexed and controlled by a single acquisition unit. The analyzers were tested to have less than 2% variability from unit to unit due to tight manufacturing tolerances. The main sensor assembly consists of a 300 mm disk to mimic a semiconductor wafer and the plasma sampling orifices of each sensor are flush with disk surface. This device is placed directly on top of the rf biased electrode, at the wafer location, in an industrial capacitively coupled plasma reactor without the need for any modification to the electrode structure. The ion energy distribution, average ion energy, and average ion flux were measured at the 13 locations over the surface of the powered electrode to determine the degree of spatial nonuniformity. The ion energy and ion flux are shown to vary by approximately 20% and 5%, respectively, across the surface of the electrode for the range of conditions investigated in this study.

36 MATERIALS SCIENCE↗

The role of group index engineering in series-connected photonic crystal microcavities for high density sensor microarrays

We experimentally demonstrate an efficient and robust method for series connection of photonic crystal microcavities that are coupled to photonic crystal waveguides in the slow light transmission regime. We demonstrate that group index taper engineering provides excellent optical impedance matching between the input and output strip waveguides and the photonic crystal waveguide, a nearly flat transmission over the entire guided mode spectrum and clear multi-resonance peaks corresponding to individual microcavities that are connected in series. Series connected photonic crystal microcavities are further multiplexed in parallel using cascaded multimode interference power splitters to generate a high density silicon nanophotonic microarray comprising 64 photonic crystal microcavity sensors, all of which are interrogated simultaneously at the same instant of time.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A portable time-domain LED fluorimeter for nanosecond fluorescence lifetime measurements

Fluorescence lifetime measurements are becoming increasingly important in chemical and biological research. Time-domain lifetime measurements offer fluorescence multiplexing and improved handling of interferers compared with the frequency-domain technique. In this paper, an all solid-state, filterless, and highly portable light-emitting-diode based time-domain fluorimeter (LED TDF) is reported for the measurement of nanosecond fluorescence lifetimes. LED based excitation provides more wavelengths options compared to laser diode based excitation, but the excitation is less effective due to the uncollimated beam, less optical power, and longer latency in state transition. Pulse triggering and pre-bias techniques were implemented in our LED TDF to improve the peak optical power to over 100 mW. The proposed pulsing circuit achieved an excitation light fall time of less than 2 ns. Electrical resetting technique realized a time-gated photo-detector to remove the interference of the excitation light with fluorescence. These techniques allow the LED fluorimeter to accurately measure the fluorescence lifetime of fluorescein down to concentration of 0.5 μM. In addition, all filters required in traditional instruments are eliminated for the non-attenuated excitation/emission light power. These achievements make the reported device attractive to biochemical laboratories seeking for highly portable lifetime detection devices for developing sensors based on fluorescence lifetime changes. The device was initially validated by measuring the lifetimes of three commercial fluorophores and comparing them with reported lifetime data. It was subsequently used to characterize a ZnSe quantum dot based DNA sensor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical induction scheme for assembling nondiffracting aperiodic Vogel spirals

We introduce an experimental approach to realize aperiodic photonic lattices based on multiplexing of nondiffracting Bessel beams. This holographic optical induction scheme takes advantage of the well localized Bessel beam as a basis to assemble two-dimensional photonic lattices. We present the realization of an optically induced two-dimensional golden-angle Vogel spiral lattice, which belongs to the family of deterministic aperiodic structures. With our technique, a very broad class of photonic refractive index landscapes now becomes accessible to optical induction, which could not be realized with established distributed holographic techniques.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Optimization of magnetic switches for single particle and cell transport

The ability to manipulate an ensemble of single particles and cells is a key aim of lab-on-a-chip research; however, the control mechanisms must be optimized for minimal power consumption to enable future large-scale implementation. Recently, we demonstrated a matter transport platform, which uses overlaid patterns of magnetic films and metallic current lines to control magnetic particles and magnetic-nanoparticle-labeled cells; however, we have made no prior attempts to optimize the device geometry and power consumption. Here, we provide an optimization analysis of particle-switching devices based on stochastic variation in the particle's size and magnetic content. These results are immediately applicable to the design of robust, multiplexed platforms capable of transporting, sorting, and storing single cells in large arrays with low power and high efficiency.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Triple plasmon resonance of bimetal nanoshell

In this paper, light absorption spectra properties of a bimetal multilayer nanoshell based on quasi-static approach are investigated. Comparing with silver-dielectric-silver and silver-dielectric-gold nanoshells, gold-dielectric-silver nanoshells have three intense and separated plasmon peaks which are more suitable for multiplex biosensing. Calculations show that relatively small thickness of outer silver shell and large dielectric constant of middle dielectric layer of gold-dielectric-silver nanoshell are suitable to obtain the triple plasmon resonance.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

All-optical switching in optically induced nonlinear waveguide couplers

We experimentally demonstrate all-optical vortex switching in nonlinear coupled waveguide arrays optically induced in photorefractive media. Our technique is based on multiplexing of nondiffracting Bessel beams to induce various types of waveguide configurations. Using double- and quadruple-well potentials, we demonstrate precise control over the coupling strength between waveguides, the linear and nonlinear dynamics and symmetry-breaking bifurcations of guided light, and a power-controlled optical vortex switch.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

15 Gb/s index-coupled distributed-feedback lasers based on 1.3 μm InGaAs quantum dots

The static properties and large-signal modulation capabilities of directly modulated p-doped quantum-dot distributed-feedback lasers are presented. Based on pure index gratings the devices exhibit a side-mode-suppression ratio of 58 dB and optical output powers up to 34 mW. Assisted by a broad gain spectrum, which is typical for quantum-dot material, emission wavelengths from 1290 nm to 1310 nm are covered by the transversal and longitudinal single-mode lasers fabricated from the same single wafer. Thus, these lasers are ideal devices for on-chip wavelength division multiplexing within the original-band according to the IEEE802.3ba standard. 10 Gb/s data transmission across 30 km of single mode fiber is demonstrated. The maximum error-free data rate is found to be 15 Gb/s.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Dual-angle, self-calibrating Thomson scattering measurements in RFX-MOD

In the multipoint Thomson scattering (TS) system of the RFX-MOD experiment the signals from a few spatial positions can be observed simultaneously under two different scattering angles. In addition the detection system uses optical multiplexing by signal delays in fiber optic cables of different length so that the two sets of TS signals can be observed by the same polychromator. Owing to the dependence of the TS spectrum on the scattering angle, it was then possible to implement self-calibrating TS measurements in which the electron temperature T{sub e}, the electron density n{sub e} and the relative calibration coefficients of spectral channels sensitivity C{sub i} were simultaneously determined by a suitable analysis of the two sets of TS data collected at the two angles. The analysis has shown that, in spite of the small difference in the spectra obtained at the two angles, reliable values of the relative calibration coefficients can be determined by the analysis of good S/N dual‑angle spectra recorded in a few tens of plasma shots. This analysis suggests that in RFX-MOD the calibration of the entire set of TS polychromators by means of the similar, dual-laser (Nd:YAG/Nd:YLF) TS technique, should be feasible.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The simulation and improved design of tunable channel drop filter using hexagonal photonic crystal ring resonator

In this paper, we have proposed a new design of tunable two dimensional (2D) photonic crystal (PhC) channel drop filter (CDF) using ring resonators. The increasing interest in photonic integrated circuits (PIC's) and the increasing use of all-optical fiber networks as backbones for global communication systems have been based in large part on the extremely wide optical transmission bandwidth provided by dielectric materials. Based on the analysis we present novel photonic crystal channel drop filters. Simulations demonstrate that these filters exhibit ideal transfer characteristics. Channel dropping filters (CDF's) that access one channel of a wavelength division multiplexed (WDM) signal while leaving other channels undisturbed are essential components of PIC's and optical communication systems. In this paper we have investigated such parameters which have an effect on resonant wavelength in this Channel Drop Filter, such as dielectric constant of inner, coupling, adjacent and whole rods of the structure. The dimensions of these structures are taken as 20a×19a and the area of the proposed structure is about 125.6μm{sup 2}; therefore this structure can be used in the future photonic integrated circuits. While using this design the dropping efficiency at the resonance of single ring are 100%. The spectrum of the power transmission is obtained with finite difference time domain (FDTD) method. FDTD method is the most famous method for PhC analysis. In this paper the dielectric rods have a dielectric constant of 10.65, so the refractive index is 3.26 and radius r=0.213a is located in air, where a is a lattice constant. In this we have used five scatter rods for obtaining more coupling efficiency; radius of scatter rods is set to 0.215a. The proposed structure is simulated with OptiFDTD.v.8.0 software, the different dielectric constant of rods equal to ε{sub r}−0.4, ε{sub r} and ε{sub r}+0.4 at wavelength of 1570 nm.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗