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At least 1,063 records · Page 59

Feasibility study of molecular memory device based on DNA using methylation to store information

DNA, because of its robustness and dense information storage capability, has been proposed as a potential candidate for next-generation storage media. However, encoding information into the DNA sequence requires molecular synthesis technology, which to date is costly and prone to synthesis errors. Reading the DNA strand information is also complex. Ideally, DNA storage will provide methods for modifying stored information. Here, we conduct a feasibility study investigating the use of the DNA 5-methylcytosine (5mC) methylation state as a molecular memory to store information. We propose a new 1-bit memory device and study, based on the density functional theory and non-equilibrium Green's function method, the feasibility of electrically reading the information. Our results show that changes to methylation states lead to changes in the peak of negative differential resistance which can be used to interrogate memory state. Our work demonstrates a new memory concept based on methylation state which can be beneficial in the design of next generation DNA based molecular electronic memory devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Development of plasma bolometers using fiber-optic temperature sensors

Measurements of radiated power in magnetically confined plasmas are important for exhaust studies in present experiments and expected to be a critical diagnostic for future fusion reactors. Resistive bolometer sensors have long been utilized in tokamaks and helical devices but suffer from electromagnetic interference (EMI). Results are shown from initial testing of a new bolometer concept based on fiber-optic temperature sensor technology. A small, 80 μm diameter, 200 μm long silicon pillar attached to the end of a single mode fiber-optic cable acts as a Fabry–Pérot cavity when broadband light, λ{sub o} ∼ 1550 nm, is transmitted along the fiber. Changes in temperature alter the optical path length of the cavity primarily through the thermo-optic effect, resulting in a shift of fringes reflected from the pillar detected using an I-MON 512 OEM spectrometer. While initially designed for use in liquids, this sensor has ideal properties for use as a plasma bolometer: a time constant, in air, of ∼150 ms, strong absorption in the spectral range of plasma emission, immunity to local EMI, and the ability to measure changes in temperature remotely. Its compact design offers unique opportunities for integration into the vacuum environment in places unsuitable for a resistive bolometer. Using a variable focus 5 mW, 405 nm, modulating laser, the signal to noise ratio versus power density of various bolometer technologies are directly compared, estimating the noise equivalent power density (NEPD). Present tests show the fiber-optic bolometer to have NEPD of 5-10 W/m{sup 2} when compared to those of the resistive bolometer which can achieve <0.5 W/m{sup 2} in the laboratory, but this can degrade to 1-2 W/m{sup 2} or worse when installed on a tokamak. Concepts are discussed to improve the signal to noise ratio of this new fiber-optic bolometer by reducing the pillar height and adding thin metallic coatings, along with improving the spectral resolution of the interrogator.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Point source atom interferometry with a cloud of finite size

We demonstrate a two axis gyroscope by the use of light pulse atom interferometry with an expanding cloud of atoms in the regime where the cloud has expanded by 1.1–5 times its initial size during the interrogation. Rotations are measured by analyzing spatial fringe patterns in the atom population obtained by imaging the final cloud. The fringes arise from a correlation between an atom's initial velocity and its final position. This correlation is naturally created by the expansion of the cloud, but it also depends on the initial atomic distribution. We show that the frequency and contrast of these spatial fringes depend on the details of the initial distribution and develop an analytical model to explain this dependence. We also discuss several challenges that must be overcome to realize a high-performance gyroscope with this technique.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Development and characterization of a high yield transportable pulsed neutron source with efficient and compact pulsed power system

The results of characterization experiments carried out on a newly developed dense plasma focus device based intense pulsed neutron source with efficient and compact pulsed power system are reported. Its high current sealed pseudospark switch based low inductance capacitor bank with maximum stored energy of ∼10 kJ is segregated into four modules of ∼2.5 kJ each and it cumulatively delivers peak current in the range of 400 kA–600 kA (corresponding to charging voltage range of 14 kV–18 kV) in a quarter time period of ∼2 μs. The neutron yield performance of this device has been optimized by discretely varying deuterium filling gas pressure in the range of 6 mbar–11 mbar at ∼17 kV/550 kA discharge. At ∼7 kJ/8.5 mbar operation, the average neutron yield has been measured to be in the order of ∼4 × 10{sup 9} neutrons/pulse which is the highest ever reported neutron yield from a plasma focus device with the same stored energy. The average forward to radial anisotropy in neutron yield is found to be ∼2. The entire system is contained on a moveable trolley having dimensions 1.5 m × 1 m × 0.7 m and its operation and control (up to the distance of 25 m) are facilitated through optically isolated handheld remote console. The overall compactness of this system provides minimum proximity to small as well as large samples for irradiation. The major intended application objective of this high neutron yield dense plasma focus device development is to explore the feasibility of active neutron interrogation experiments by utilization of intense pulsed neutron sources.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A high precision gas flow cell for performing in situ neutron studies of local atomic structure in catalytic materials

Gas-solid interfaces enable a multitude of industrial processes, including heterogeneous catalysis; however, there are few methods available for studying the structure of this interface under operating conditions. Here, we present a new sample environment for interrogating materials under gas-flow conditions using time-of-flight neutron scattering under both constant and pulse probe gas flow. Outlined are descriptions of the gas flow cell and a commissioning example using the adsorption of N 2 by Ca-exchanged zeolite-X (Na 78–2x Ca x Al 78 Si 144 O 384 ,x ≈ 38). We demonstrate sensitivities to lattice contraction and N 2 adsorption sites in the structure, with both static gas loading and gas flow. A steady-state isotope transient kinetic analysis of N 2 adsorption measured simultaneously with mass spectrometry is also demonstrated. In the experiment, the gas flow through a plugged-flow gas-solid contactor is switched between 15 N 2 and 14 N 2 isotopes at a temperature of 300 K and a constant pressure of 1 atm; the gas flow and mass spectrum are correlated with the structure factor determined from event-based neutron total scattering. As a result, available flow conditions, sample considerations, and future applications are discussed.

36 MATERIALS SCIENCE↗

Time-resolved, dual heterodyne phase collection transient grating spectroscopy

The application of optical heterodyne detection for transient grating spectroscopy (TGS) using a fixed, binary phase mask often relies on taking the difference between signals captured at multiple heterodyne phases. To date, this has been accomplished by manually controlling the heterodyne phase between measurements with an optical flat. In this letter, an optical configuration is presented which allows for collection of TGS measurements at two heterodyne phases concurrently through the use of two independently phase controlled interrogation paths. This arrangement allows for complete, heterodyne amplified TGS measurements to be made in a manner not constrained by a mechanical actuation time. Measurements are instead constrained only by the desired signal-to-noise ratio. A temporal resolution of between 1 and 10 s, demonstrated here on single crystal metallic samples, will allow TGS experiments to be used as an in-situ, time-resolved monitoring technique for many material processing applications.

36 MATERIALS SCIENCE↗

Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations

Many of water’s remarkable properties arise from its tendency to form an intricate and robust hydrogen bond network. Understanding the dynamics that govern this network is fundamental to elucidating the behavior of pure water and water in biological and physical systems. In ultrafast nonlinear infrared experiments, the accessible time scales are limited by water’s rapid vibrational relaxation (1.8 ps for dilute HOD in H 2 O), precluding interrogation of slow hydrogen bond evolution in non-bulk systems. Here in this paper, hydrogen bonding dynamics in bulk D 2 O were studied from the perspective of the much longer lived (36.2 ps) CN stretch mode of selenocyanate (SeCN-) using polarization selective pump-probe (PSPP) experiments, two-dimensional infrared (2D IR) vibrational echo spectroscopy, and molecular dynamics simulations. The simulations make use of the empirical frequency mapping approach, applied to SeCN - for the first time. The PSPP experiments and simulations show that the orientational correlation function decays via fast (2.0 ps) restricted angular diffusion (wobbling-in-a-cone) and complete orientational diffusive randomization (4.5 ps). Spectral diffusion, quantified in terms of the frequency-frequency correlation function, occurs on two time scales. The initial 0.6 ps time scale is attributed to small length and angle fluctuations of the hydrogen bonds between water and SeCN - . The second 1.4 ps measured time scale, identical to that for HOD in bulk D 2 O, reports on the collective reorganization of the water hydrogen bond network around the anion. Lastly, the experiments and simulations provide details of the anion-water hydrogen bonding and demonstrate that SeCN- is a reliable vibrational probe of the ultrafast spectroscopy of water.

14 SOLAR ENERGY↗

Delocalization and stretch-bend mixing of the HOH bend in liquid water

Liquid water’s rich sub-picosecond vibrational dynamics arise from the interplay of different high- and low-frequency modes evolving in a strong yet fluctuating hydrogen bond network. Recent studies of the OH stretching excitations of H 2 O indicate that they are delocalized over several molecules, raising questions about whether the bending vibrations are similarly delocalized. In this paper, we take advantage of an improved 50 fs time-resolution and broadband infrared (IR) spectroscopy to interrogate the 2D IR lineshape and spectral dynamics of the HOH bending vibration of liquid H2O. Indications of strong bend-stretch coupling are observed in early time 2D IR spectra through a broad excited state absorption that extends from 1500 cm -1 to beyond 1900 cm -1 , which corresponds to transitions from the bend to the bend overtone and OH stretching band between 3150 and 3550 cm -1 . Pump-probe measurements reveal a fast 180 fs vibrational relaxation time, which results in a hot-ground state spectrum that is the same as observed for water IR excitation at any other frequency. The fastest dynamical time scale is 80 fs for the polarization anisotropy decay, providing evidence for the delocalized or excitonic character of the bend. Finally, normal mode analysis conducted on water clusters extracted from molecular dynamics simulations corroborate significant stretch-bend mixing and indicate delocalization of δ HOH on 2-7 water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Perspective: Size selected clusters for catalysis and electrochemistry

We report that size-selected clusters containing a handful of atoms may possess noble catalytic properties different from nano-sized or bulk catalysts. Size- and composition-selected clusters can also serve as models of the catalytic active site, where an addition or removal of a single atom can have a dramatic effect on their activity and selectivity. In this Perspective, we provide an overview of studies performed under both ultra-high vacuum and realistic reaction conditions aimed at the interrogation, characterization and understanding of the performance of supported size-selected clusters in heterogeneous and electrochemical reactions, which address the effects of cluster size, cluster composition, cluster-support interactions and reaction conditions, the key parameters for the understanding and control of catalyst functionality. Computational modelling based on density functional theory sampling of local minima and energy barriers or ab initio Molecular Dynamics simulations is an integral part of this research by providing fundamental understanding of the catalytic processes at the atomic level, as well as by predicting new materials compositions which can be validated in experiments. Lastly, we discuss approaches which aim at the scale up of the production of well-defined clusters for use in real world applications.

36 MATERIALS SCIENCE↗

Conformational explosion: Understanding the complexity of short chain para -dialkylbenzene potential energy surfaces

The single-conformation ultraviolet and infrared spectroscopy of three short-chain para-dialkylbenzenes (para-diethylbenzene, para-dipropylbenzene, and para-dibutylbenzene) is reported for the jet-cooled, isolated molecules. The present study builds off previous work on single-chain n-alkylbenzenes, where an anharmonic local mode Hamiltonian method was developed to account for stretch-bend Fermi resonance in the alkyl CH stretch region [D. P. Tabor et al., J. Chem. Phys. 144, 224310 (2016)]. The jet-cooled molecules are interrogated using laser-induced fluorescence (LIF) excitation, fluorescence dip infrared spectroscopy, and dispersed fluorescence. The LIF spectra in the S1 ← S0 origin region show a dramatic increase in the number of resolved transitions with increasing length of the alkyl chains, reflecting an explosion in the number of unique low-energy conformations formed when two independent alkyl chains are present. Since the barriers to isomerization of the alkyl chain are similar in size, this results in an “egg carton” shaped potential energy surface. A combination of electronic frequency shift and alkyl CH stretch infrared spectra is used to generate a consistent set of conformational assignments. Using these experimental techniques in conjunction with computational methods, subsets of origin transitions in the LIF excitation spectrum can be classified into different conformational families. Two conformations are resolved in para-diethylbenzene, seven in para-dipropylbenzene, and about nineteen in para-dibutylbenzene. These chains are largely independent of each other as there are no new single-chain conformations induced by the presence of a second chain. A cursory LIF excitation scan of para-dioctylbenzene shows a broad congested spectrum at frequencies consistent with interactions of alkyl chains with the phenyl π cloud

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Study of the properties of thin Li films and their relationship with He plasmas using ion beam analysis in the DIONISOS experiment

Plasma facing component (PFC) conditioning dramatically affects plasma performance in magnetic confinement fusion experiments. Lithium (Li) has been used in several machines to condition PFC with subsequent improvements to plasma performance. Multiple studies have investigated the interactions of Li with deuterium (D) and oxygen (O) in order to ascertain the mechanisms behind the enhanced plasma performance. Ion Beam Analysis (IBA) is a useful tool to interrogate PFC surfaces as they interact with plasmas. Dynamics of ion implantation and sputtering of surfaces (DIONISOS) is a linear plasma device, capable of generating discharges with fluxes ~10 21 m -2 s -1 and Te ~6 eV, coupled to an ion accelerator. DIONISOS is capable of analyzing samples using Elastic Recoil Detection (ERD) and Rutherford Backscattering Spectroscopy (RBS) during plasma exposures. The facility has been equipped with a Li deposition system for evaporation of thin coatings on different substrates. The evaporator enables real time ERD and RBS measurements of deposition and erosion of Li coatings on different substrates and the interaction of the Li with the vacuum and plasma. Considerations for ERD, e.g., ion species, energy, and data acquisition frequency, are presented. Furthermore, this work is the basis for further investigation of He, H, and D retention in solid and liquid Li.

47 OTHER INSTRUMENTATION↗

Time-of-flight neutron total scattering with applied electric fields: Ex situ and in situ studies of ferroelectric materials

Characterizing the structural response of functional materials (e.g., piezoelectrics and ferroelectrics) to electric fields is key for the creation of structure-property relationships. Here in this paper, we present a new sample environment and data reduction routines which allow the measurement of time-of-flight neutron total scattering during the in situ or ex situ application of high voltage (<10 kV) to a sample. Instead of utilizing the entire detector space of the diffractometer, only selected regions of detector pixels with scattering at the desired angle to the sample electric field are interrogated, which allows the generation of orientation-dependent reciprocal space patterns and real-space pair distribution functions (PDFs). We demonstrate the method using the relaxor ferroelectric Na 1/2 Bi 1/2 TiO 3 and observe lattice expansion parallel and contraction perpendicular to the electric field for both in situ or ex situ experiments, revealing the irreversible nature of the local scale structural changes to this composition. Additionally, changes in the distributions of nearest neighbor metal-oxygen bond lengths are observed, which have been difficult to observe in previously measured analogous orientation-dependent X-ray PDFs. Lastly, considerations related to sample positioning and background subtraction are discussed, and future research directions are suggested.

36 MATERIALS SCIENCE↗

Pulsed laser deposition films from a Ba 2 FeMoO 6 target onto SrTiO 3 [001]: Chemical and magnetic inhomogeneity

Pulsed laser deposition films from Ba 2 FeMoO 6 (BFMO) targets onto SrTiO 3 [001] (STO) substrates have been reported previously to have non-zero magnetism at 300 K, a majority of magnetic ordering at 240 K that is less than the 370 K ordering temperature of polycrystalline BFMO, and suppressed saturation magnetization compared to polycrystalline BFMO. To interrogate these previously reported observations of BFMO on STO, here we have used a combination of x-ray diffraction, atomic force microscopy, x-ray and neutron reflectivity, and x-ray photoelectron spectroscopy that shows inhomogeneities. The present results show off-stoichiometry on the A-site by incorporation of Sr from the substrate and on the B-site to have %Fe/%Mo > 1 by evolution of BaMoO 4 . There is an enhanced ordering temperature and magnetic response nearer to the SrTiO 3 interface compared to the air interface. Depth dependent strain and microstructure are needed to explain the magnetic response. Finally, holistic considerations and implications are also discussed.

36 MATERIALS SCIENCE↗

Dual laser holography for in situ measurement of plasma facing component erosion (invited)

A digital holography (DH) surface erosion/deposition diagnostic is being developed for 3D imaging of plasma facing component surfaces in situ and in real time. Digital holography is a technique that utilizes lasers reflected from a material surface to form an interferogram, which carries information about the topology of the surface when reconstructed. As described, dual CO 2 lasers at 9.271 and 9.250 μm wavelengths illuminate the interrogated surface (at a distance of ~1 m) in a region of ~1 cm × 1 cm. The surface feature resolution is ~0.1 mm in the plane of the surface, and the depth resolution ranges from ~0.0001 to ~2 mm perpendicular to the surface. The depth resolution lower limit is set by single-laser and detector optical limitations, while the upper limit is determined by 2π phase ambiguity of the dual-laser synthetic wavelength. Measurements have been made “on the bench” to characterize the single-laser and dual-laser DH configurations utilizing standard resolution targets and material targets that were previously exposed to high flux plasmas in either the Prototype Material Plasma Exposure eXperiment (Proto-MPEX) or the electro-thermal (ET) arc source. Typical DH measurements were made with 0.03 ms integration with an IR camera that can be framed at rates approaching 1.5 kHz. Finally, the DH diagnostic system is progressing toward in situ measurements of plasma erosion/deposition either on Proto-MPEX or the ET arc source.

47 OTHER INSTRUMENTATION↗

Multiplexed characterization of complex gas-phase mixtures combining chirped-pulse Fourier transform microwave spectroscopy and VUV photoionization time-of-flight mass spectrometry

We examine details of the design and operation of a single apparatus that combines Chirped-Pulse Fourier Transform Microwave (CP-FTMW) spectroscopy with vacuum ultraviolet (VUV) photoionization Time-of-Flight Mass Spectrometry (TOFMS). The supersonic expansion used for cooling samples is interrogated first by passing through the region between two microwave horns capable of broadband excitation and detection in the 2-18 GHz frequency region of the microwave. After passing through this region, the expansion is skimmed to form a molecular beam, before being probed with 118 nm (10.5 eV) single-photon VUV photoionization in a linear time-of-flight mass spectrometer. The two detection schemes are powerfully complementary to one another. CP-FTMW detects all components with significant permanent dipole moments. Rotational transitions provide high-resolution structural data. VUV TOFMS provides a gentle and general method for ionizing all components of a gas phase mixture with ionization thresholds below 10.5 eV, providing their molecular formulae. The advantages, complementarity, and limitations of the combined methods are highlighted through findings on two gas-phase mixtures made up of (i) three furanic compounds, two of which are structural isomers of one another, and (ii) the effluent from a flash pyrolysis source with o-guaiacol as the precursor.

47 OTHER INSTRUMENTATION↗

A new framework for X-ray photon correlation spectroscopy analysis from polycrystalline materials

Here, we report a new analytical framework for interpreting data from X-ray photon correlation spectroscopy (XPCS) measurements on polycrystalline materials characterized by strong scattering intensity variations at fixed wavevector magnitude (i.e., anisotropic scattering). Currently, no analytical method exists for the interpretation of the time-dependent anisotropic scattering from such materials. The framework is applied to interrogate the dynamics of a spherical micelle-forming diblock copolymer melt below the order-disorder transition, wherein finite size grains of micellar body-centered cubic structure produce anisotropic scattering. A wealth of analytical information is recovered from a simple measurement, including distributions of relaxation times and speeds associated with micelles within grains. The findings of this study demonstrate the efficacy of this new analytical method, which may be readily adapted for application to a variety of materials and systems.

47 OTHER INSTRUMENTATION↗

Accuracy of tip-sample interaction measurements using dynamic atomic force microscopy techniques: Dependence on oscillation amplitude, interaction strength, and tip-sample distance

Atomic force microscopy (AFM) is a versatile surface characterization method that can map a sample’s topography with high spatial resolution while simultaneously interrogating its surface chemistry through the site-specific high-resolution quantification of the forces acting between the sample and the probe tip. Thanks to considerable advances in AFM measurement technology, such local measurements of chemical properties have gained much popularity in recent years. To this end, dynamic AFM methodologies are implemented where either the oscillation frequency or the oscillation amplitude and phase of the vibrating cantilever are recorded as a function of tip-sample distance and subsequently converted to reflect tip-sample forces or interaction potentials. Such conversion has, however, been shown to produce non-negligible errors when applying the most commonly used mathematical conversion procedures if oscillation amplitudes are of the order of the decay length of the interaction. Extending on these earlier findings, the computational study presented in this paper reveals that the degree of divergence from actual values may also critically depend on both the overall strength of tip-sample interaction and the distance at which the interaction is obtained. These systematic errors can, however, be effectively eliminated by using oscillation amplitudes that are sufficiently larger than the decay length of the interaction potential.

Electrical properties and parameters↗

Propagating molecular rotational coherences through single-frequency pulses in the strong field regime

In the weak-field limit in which microwave spectroscopy is typically carried out, an application of a single-frequency pulse that is resonant with a molecular transition will create a coherence between the pair of states involved in the rotational transition, producing a free-induction decay (FID) that, after Fourier transform, produces a molecular signal at that same resonance frequency. With the advent of chirped-pulse Fourier transform microwave methods, the high-powered amplifiers needed to produce broadband microwave spectra also open up other experiments that probe the molecular response in the high-field regime. This paper describes a series of experiments involving resonant frequency pulses interrogating jet-cooled molecules under conditions of sufficient power to Rabi oscillate the two-state system through many Rabi cycles. The Fourier-transformed FID shows coherent signal not only at the applied resonant frequency but also at a series of transitions initially connected to the original one by sharing an upper or lower level with it. As the duration of the single-frequency excitation is increased from 250 to 1500 ns, the number of observed off-resonant, but dipole-allowed, molecular coherences grow. The phenomenon is quite general, having been demonstrated in Z-phenylvinylnitrile, E-phenylvinylnitrile (E-PVN), benzonitrile, guaiacol, and 4-pentynenitrile. In E-PVN, the highest power/longest pulse duration, coherent signal is also present at energetically nearby but not directly connected transitions. Even in molecular samples containing more than one independent species, only transitions due to the single species responsible for the original resonant transition are present. Here, we develop a time-dependent model of the molecular/photon system and use it in conjunction with the experiment to test possible sources of the phenomenon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗