ALBERT

Description: A glassy dilute glycerol-water solution undergoes a mutual polyamorphic transition relating to the transition between high- and low-density amorphous ices of solvent water. The polyamorphic transition behavior depends on the glycerol concentration, indicating that the glycerol affects the water polyamorphism. Here, we used the glassy dilute glycerol-water solution of the solute molar fraction of 0.07 and examined the effect of the polyamorphic change in solvent water on the molecular vibrations of glycerol via Raman spectroscopy. It is found that the molecular vibration of glycerol in high-density liquid like solvent water is different from that in the low-density liquid like solvent water and that the change in the molecular vibration of glycerol is synchronized with the polyamorphic transition of solvent water. The dynamical change of the solute molecule relates to the polyamorphic state of solvent water. This result suggests that the polyamorphic fluctuation of water structure emanated from the presumed liquid-liquid critical point plays an important role for the function of aqueous solution under an ambient condition such as the conformational stability of solute, the functional expression of solute, and so on.

Description: We propose a new on-the-fly kinetic Monte Carlo (KMC) method that is based on exhaustive potential energy surface searching carried out with the global reaction route mapping (GRRM) algorithm. Starting from any given equilibrium state, this GRRM-KMC algorithm performs a one-step GRRM search to identify all surrounding transition states. Intrinsic reaction coordinate pathways are then calculated to identify potential subsequent equilibrium states. Harmonic transition state theory is used to calculate rate constants for all potential pathways, before a standard KMC accept/reject selection is performed. The selected pathway is then used to propagate the system forward in time, which is calculated on the basis of 1st order kinetics. The GRRM-KMC algorithm is validated here in two challenging contexts: intramolecular proton transfer in malonaldehyde and surface carbon diffusion on an iron nanoparticle. We demonstrate that in both cases the GRRM-KMC method is capable of reproducing the 1st order kinetics observed during independent quantum chemical molecular dynamics simulations using the density-functional tight-binding potential.

Description: Resonantly enhanced multiphoton ionization via the E F 1 Σ g + , v ′ = 6 double-well state has been used to probe the energy region below the third dissociation limit of H 2 where several high vibrational levels of the 4 1 Σ u + state are expected. Theoretical ab initio potential energy curves for this state predict a deep inner well and shallow outer well where vibrational levels above v = 8 are expected to exhibit the double-well character of the state. Since the 4 1 Σ u + state has f -state character, transitions to it from the ground state are nominally forbidden. However, the d character of the outer well of the E F 1 Σ g + state allows access to this state. We report observations of transitions to the v = 9–12 levels of the 4 1 Σ u + state and compare their energies to predicted energies calculated from an ab initio potential energy curve with adiabatic corrections. Assignments are based on measured energies and linewidths, rotational constants, and expected transition strengths. The amount of agreement between the predicted values and the observations is mixed, with the largest discrepancies arising for the v = 9 level, owing to strong nonadiabatic electronic mixing in this energy region.

Description: The photodissociation dynamics of the methyl perthiyl radical (CH 3 SS) have been investigated using fast-beam coincidence translational spectroscopy. Methyl perthiyl radicals were produced by photodetachment of the CH 3 SS − anion followed by photodissociation at 248 nm (5.0 eV) and 193 nm (6.4 eV). Photofragment mass distributions and translational energy distributions were measured at each dissociation wavelength. Experimental results show S atom loss as the dominant (96%) dissociation channel at 248 nm with a near parallel, anisotropic angular distribution and translational energy peaking near the maximal energy available to ground state CH 3 S and S fragments, indicating that the dissociation occurs along a repulsive excited state. At 193 nm, S atom loss remains the major fragmentation channel, although S 2 loss becomes more competitive and constitutes 32% of the fragmentation. The translational energy distributions for both channels are very broad at this wavelength, suggesting the formation of the S 2 and S atom products in several excited electronic states.

Description: An aerodynamic levitator with carbon dioxide laser beam heating was integrated with a hermetically sealed controlled atmosphere chamber and sample handling mechanism. The system enabled containment of radioactive samples and control of the process atmosphere chemistry. The chamber was typically operated at a pressure of approximately 0.9 bars to ensure containment of the materials being processed. Samples 2.5-3 mm in diameter were levitated in flowing gas to achieve containerless conditions. Levitated samples were heated to temperatures of up to 3500 °C with a partially focused carbon dioxide laser beam. Sample temperature was measured using an optical pyrometer. The sample environment was integrated with a high energy (100 keV) x-ray synchrotron beamline to enable in situ structure measurements to be made on levitated samples as they were heated, melted, and supercooled. The system was controlled from outside the x-ray beamline hutch by using a LabVIEW program. Measurements have been made on hot solid and molten uranium dioxide and binary uranium dioxide-zirconium dioxide compositions.

Description: We have developed an optical Absolute Distance Meter (ADM) based on the measurement of the phase accumulated by a Radio Frequency wave during its propagation in the air by a laser beam. In this article, the ADM principle will be described and the main results will be presented. In particular, we will emphasize how the choice of an appropriate photodetector can significantly improve the telemeter performances by minimizing the amplitude to phase conversion. Our prototype, tested in the field, has proven its efficiency with a resolution better than 15 μm for a measurement time of 10 ms and distances up to 1.2 km.

Description: 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 μ m thick, 9 × 7 cm 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.

Description: We have investigated the thickness-dependent transport properties of La 1/3 Sr 2/3 FeO 3 thin films grown on SrTiO 3 (001) and (111) substrates. At a thickness of ∼40 nm, both films show a clear transition in resistivity associated with the characteristic charge disproportionation at approximately 190 K. The transition temperature of the charge disproportionation is nearly unchanged with decreasing film thickness down to a certain thickness of ∼13 nm for both orientations, while the change in resistivity gradually decreases. Below this thickness, the transition becomes unclear, strongly suggesting the suppression of the charge disproportionation at the critical thickness of ∼13 nm. Furthermore, there is no significant difference in the thickness dependence of La 1/3 Sr 2/3 FeO 3 thin films between the (001) and (111) orientations. The negligible crystallographic-orientation dependence may reflect the isotropic nature for the domain of charge disproportionation states in La 1/3 Sr 2/3 FeO 3 .

Description: Titanium oxide (TiO x ) has attracted a lot of attention as an active material for resistive random access memory (RRAM), due to its versatility and variety of possible crystal phases. Although existing RRAM materials have demonstrated impressive characteristics, like ultra-fast switching and high cycling endurance, this technology still encounters challenges like low yields, large variability of switching characteristics, and ultimately device failure. Electroforming has been often considered responsible for introducing irreversible damage to devices, with high switching voltages contributing to device degradation. In this paper, we have employed Al doping for tuning the resistive switching characteristics of titanium oxide RRAM. The resistive switching threshold voltages of undoped and Al-doped TiO x thin films were first assessed by conductive atomic force microscopy. The thin films were then transferred in RRAM devices and tested with voltage pulse sweeping, demonstrating that the Al-doped devices could on average form at lower potentials compared to the undoped ones and could support both analog and binary switching at potentials as low as 0.9 V. This work demonstrates a potential pathway for implementing low-power RRAM systems.

Description: In this work, electron induced modifications on the bulk etch rate, structural and optical parameters of CR-39 polymer were studied using gravimetric, FTIR (Fourier Transform Infrared) and UV–vis (Ultraviolet–Visible) techniques, respectively. CR-39 samples were irradiated with 10 MeV electron beam for different durations to have the absorbed doses of 1, 10, 550, 5500, 16 500, and 55 000 kGy. From the FTIR analysis, the peak intensities at different bands were found to be changing with electron dose. A few peaks were observed to shift at high electron doses. From the UV-vis analysis, the optical band gaps for both direct and indirect transitions were found to be decreasing with the increase in electron dose whereas the opacity, number of carbon atoms in conjugation length, and the number of carbon atoms per cluster were found to be increasing. The bulk etch rate was observed to be increasing with the electron dose. The primary objective of this investigation was to study the response of CR-39 to high electron doses and to determine a suitable pre-irradiation condition. The results indicated that, the CR-39 pre-irradiated with electrons can have better sensitivity and thus can be potentially applied for neutron dosimetry.

Description: Low temperature thermal to electrical energy converters have the potential to provide a route for recovering waste energy. In this paper, we propose a new configuration of a thermal harvester that uses a naturally driven thermal oscillator free of mechanical motion and operates between a hot heat source and a cold heat sink. The system exploits a heat induced liquid-vapour transition of a working fluid as a primary driver for a pyroelectric generator. The two-phase instability of a fluid in a closed looped capillary channel of an oscillating heat pipe (OHP) creates pressure differences which lead to local high frequency temperature oscillations in the range of 0.1–5 K. Such temperature changes are suitable for pyroelectric thermal to electrical energy conversion, where the pyroelectric generator is attached to the adiabatic wall of the OHP, thereby absorbing thermal energy from the passing fluid. This new pyroelectric-oscillating heat pipe (POHP) assembly of a low temperature generator continuously operates across a spatial heat source temperature of 55 °C and a heat sink temperature of 25 °C, and enables waste heat recovery and thermal energy harvesting from small temperature gradients at low temperatures. Our electrical measurements with lead zirconate titanate (PZT) show an open circuit voltage of 0.4 V (AC) and with lead magnesium niobate–lead titanate (PMN-PT) an open circuit voltage of 0.8 V (AC) at a frequency of 0.45 Hz, with an energy density of 95 pJ cm −3 for PMN-PT. Our novel POHP device therefore has the capability to convert small quantities of thermal energy into more desirable electricity in the nW to mW range and provides an alternative to currently used batteries or centralised energy generation.

Description: Electrode materials selection guidelines for oxide-based memory devices are constructed from the combined knowledge of observed device operation characteristics, ab-initio calculations, and nano-material characterization. It is demonstrated that changing the top electrode material from Ge to Cr to Ta in the Ta 2 O 5 -based memory devices resulted in a reduction of the operation voltages and current. Energy Dispersed X-ray (EDX) Spectrometer analysis clearly shows that the different top electrode materials scavenge oxygen ions from the Ta 2 O 5 memory layer at various degrees, leading to different oxygen vacancy concentrations within the Ta 2 O 5 , thus the observed trends in the device performance. Replacing the Pt bottom electrode material with CMOS compatible materials (Ru and Ir) further reduces the power consumption and can be attributed to the modification of the Schottky barrier height and oxygen vacancy concentration at the electrode/oxide interface. Both trends in the device performance and EDX results are corroborated by the ab-initio calculations which reveal that the electrode material tunes the oxygen vacancy concentration via the oxygen chemical potential and defect formation energy. This experimental-theoretical approach strongly suggests that the proper selection of CMOS compatible electrode materials will create the critical oxygen vacancy concentration to attain low power memory performance.

Description: Thus far, despite many investigations have been carried out for photo-triggered drug delivery systems, most of them suffer from an intrinsic drawback of without real-time monitoring mechanism. Incident intensity of light is a feasible parameter to monitor the drug release profiles. However, it is difficult to measure the incident laser power irradiated onto the photo-triggered carriers in drug delivery systems during in vivo therapy. We design an online measurement method based on the fluorescence intensity ratio (FIR) technique through upconversion nanoparticles. FIR value varies with temperature of sample due to the thermal effect induced by the incident laser, which validates the laser power measurement. Effects of rare earth doping concentration, as well as experimental conditions including laser spots and wavelengths on the measurement behavior were also investigated.

Description: Several candidate phenomenological expressions are studied for self-rippling energy that drives ripple formation of free single-layer graphene sheets. One phenomenological expression is admitted, while all others are rejected because they cannot admit stable periodic ripple mode. The admitted phenomenological expression contains two terms: one quadratic term which acts like a compressive force and has a destabilizing effect, and another fourth-order term which acts like a nonlinear elastic foundation and has a stabilizing effect. The two associated coefficients depend on specific mechanism of self-rippling and can be determined based on observed wavelength and amplitude of ripple mode. Based on the admitted expression, the effect of an applied force on ripple formation is studied. The present model predicts that the rippling can be controlled or even suppressed with an applied tensile force or collapsed into narrow wrinkles (of deformed wavelengths down to around 2 nm) under an applied compressive force, and the estimated minimum tensile strain to suppress rippling is in remarkable agreement with some known data. Our results show that self-rippling energy dominates ripple formation of sufficiently long free graphene ribbons, although it cannot drive self-rippling of sufficiently short free graphene ribbons. Consequently, a critical length is estimated so that self-rippling occurs only when the length of free single-layer graphene ribbons is much longer than the critical length. The estimated critical length is reasonably consistent with the known fact that self-rippling cannot occur in shorter free graphene sheets (say, of length below 20 nm).

Description: A single electron dynamic memory is designed based on the non-equilibrium dynamics of charge states in electrostatically defined metallic quantum dots. Using the orthodox theory for computing the transfer rates and a master equation, we model the dynamical response of devices consisting of a charge sensor coupled to either a single and or a double quantum dot subjected to a pulsed gate voltage. We show that transition rates between charge states in metallic quantum dots are characterized by an asymmetry that can be controlled by the gate voltage. This effect is more pronounced when the switching between charge states corresponds to a Markovian process involving electron transport through a chain of several quantum dots. By simulating the dynamics of electron transport we demonstrate that the quantum box operates as a finite-state machine that can be addressed by choosing suitable shapes and switching rates of the gate pulses. We further show that writing times in the ns range and retention memory times six orders of magnitude longer, in the ms range, can be achieved on the double quantum dot system using experimentally feasible parameters, thereby demonstrating that the device can operate as a dynamic single electron memory.

Description: Chemical vapor deposition methods were developed, using stoichiometric reactions of specialty Ge 3 H 8 and SnD 4 hydrides, to fabricate Ge 1- y Sn y photodiodes with very high Sn concentrations in the 12%–16% range. A unique aspect of this approach is the compatible reactivity of the compounds at ultra-low temperatures, allowing efficient control and systematic tuning of the alloy composition beyond the direct gap threshold. This crucial property allows the formation of thick supersaturated layers with device-quality material properties. Diodes with composition up to 14% Sn were initially produced on Ge-buffered Si(100) featuring previously optimized n -Ge/ i -Ge 1- y Sn y / p -Ge 1- z Sn z type structures with a single defected interface. The devices exhibited sizable electroluminescence and good rectifying behavior as evidenced by the low dark currents in the I-V measurements. The formation of working diodes with higher Sn content up to 16% Sn was implemented by using more advanced n -Ge 1- x Sn x / i -Ge 1- y Sn y / p -Ge 1- z Sn z architectures incorporating Ge 1- x Sn x intermediate layers ( x ∼ 12% Sn) that served to mitigate the lattice mismatch with the Ge platform. This yielded fully coherent diode interfaces devoid of strain relaxation defects. The electrical measurements in this case revealed a sharp increase in reverse-bias dark currents by almost two orders of magnitude, in spite of the comparable crystallinity of the active layers. This observation is attributed to the enhancement of band-to-band tunneling when all the diode layers consist of direct gap materials and thus has implications for the design of light emitting diodes and lasers operating at desirable mid-IR wavelengths. Possible ways to engineer these diode characteristics and improve carrier confinement involve the incorporation of new barrier materials, in particular, ternary Ge 1- x - y Si x Sn y alloys. The possibility of achieving type-I structures using binary and ternary alloy combinations is discussed in detail, taking into account the latest experimental and theoretical work on band offsets involving such materials.

Description: Temperature-dependent characteristics of GeSn light-emitting diodes with Sn composition up to 9.2% have been systematically studied. Such diodes were based on Ge/GeSn/Ge double heterostructures (DHS) that were grown directly on a Si substrate via a chemical vapor deposition system. Both photoluminescence and electroluminescence spectra have been characterized at temperatures from 300 to 77 K. Based on our theoretical calculation, all GeSn alloys in this study are indirect bandgap materials. However, due to the small energy separation between direct and indirect bandgap, and the fact that radiative recombination rate greater than non-radiative, the emissions are mainly from the direct Γ-valley to valence band transitions. The electroluminescence emissions under current injection levels from 102 to 357 A/cm 2 were investigated at 300 K. The monotonic increase of the integrated electroluminescence intensity was observed for each sample. Moreover, the electronic band structures of the DHS were discussed. Despite the indirect GeSn bandgap owing to the compressive strain, type-I band alignment was achieved with the barrier heights ranging from 11 to 47 meV.

Description: Due to their high strength and advantageous high-temperature properties, tungsten-based alloys are being considered as plasma-facing candidate materials in fusion devices. Under neutron irradiation, rhenium, which is produced by nuclear transmutation, has been found to precipitate in elongated precipitates forming thermodynamic intermetallic phases at concentrations well below the solubility limit. Recent measurements have shown that Re precipitation can lead to substantial hardening, which may have a detrimental effect on the fracture toughness of W alloys. This puzzle of sub-solubility precipitation points to the role played by irradiation induced defects, specifically mixed solute-W interstitials. Here, using first-principles calculations based on density functional theory, we study the energetics of mixed interstitial defects in W-Re, W-V, and W-Ti alloys, as well as the heat of mixing for each substitutional solute. We find that mixed interstitials in all systems are strongly attracted to each other with binding energies of −2.4 to − 3.2   eV and form interstitial pairs that are aligned along parallel first-neighbor 〈 111 〉 strings. Low barriers for defect translation and rotation enable defect agglomeration and alignment even at moderate temperatures. We propose that these elongated agglomerates of mixed-interstitials may act as precursors for the formation of needle-shaped intermetallic precipitates. This interstitial-based mechanism is not limited to radiation induced segregation and precipitation in W–Re alloys but is also applicable to other body-centered cubic alloys.

Description: The static and dynamic properties of water in small silicon-carbide and carbon nanotubes have been studied over the temperature range 100 K–298 K, using extensive molecular dynamics simulations. The computed properties include the radial distribution function, the cage correlation function, the space-time autocorrelation function, the velocity autocorrelation function, and the self-diffusivity. They all indicate that, under the conditions that we study, water does not freeze in small nanotubes; the Stokes-Einstein relation breaks down, and the self-diffusivity exhibits a transition around 230 K, very close to 228 K, the temperature at which a fragile-to-strong dynamic crossover is supposed to happen. The cage correlation function C ( t ) decays according to a stretched-exponential function, C ( t ) ∼ exp[ − ( t / τ ) β ], where τ is a relaxation time and β is a topological exponent.

Description: Feasibility of laser-cooling AlCl molecule is investigated using ab initio quantum chemistry. Potential energy curves, permanent dipole moments, and transition dipole moments for the X 1 Σ + , a 3 Π, and A 1 Π states are studied based on multi-reference configuration interaction plus Davidson corrections (MRCI+Q) method with ACVQZ basis set, spin-orbit coupling effects are considered at the MRCI+Q level. Highly diagonally distributed Franck–Condon factors ( f 00 = 0.9988 and f 11 = 0.9970) and branching ratios ( R 00 = 0.9965, R 01 = 2.85 × 10 −3 , R 02 = 6.35 × 10 −4 , and R 03 = 2.05 × 10 −6 ) for the A 1 Π 1 ( ν ′ = 0 ) → X 1 Σ 0 + + ( ν ″ = 0 ) transition are determined. A sufficiently radiative lifetime τ ( A 1 Π 1 ) = 4.99 ns is predicted for rapid laser cooling. The proposed cooling wavelength is deep in the ultraviolet region at λ 00 = 261.75 nm. Total emission rates for the a 3 Π 0 + → X 1 Σ 0 + + , a 3 Π 1 → X 1 Σ 0 + + , A 1 Π 1 → a 3 Π 0 + , and A 1 Π 1 → a 3 Π 1 transitions are particularly small (∼10 s −1 –650 s −1 ). The calculated vibrational branching loss ratio to the intermediate a 3 Π 0 + and a 3 Π 1 states can be negligible. The results imply the probability of laser cooling AlCl molecule with three-electronic-level.

Description: This paper presents an explanation based on torsionally mediated proton-spin–overall-rotation interaction for the observation of doublet hyperfine splittings in some Lamb-dip sub-millimeter-wave transitions between ground-state torsion-rotation states of E symmetry in methanol. These unexpected doublet splittings, some as large as 70 kHz, were observed for rotational quantum numbers in the range of J = 13 to 34, and K = − 2 to +3. Because they increase nearly linearly with J for a given branch, we confined our search for an explanation to hyperfine operators containing one nuclear-spin angular momentum factor I and one overall-rotation angular momentum factor J (i.e., to spin-rotation operators) and ignored both spin-spin and spin-torsion operators, since they contain no rotational angular momentum operator. Furthermore, since traditional spin-rotation operators did not seem capable of explaining the observed splittings, we constructed totally symmetric “torsionally mediated spin-rotation operators” by multiplying the E-species spin-rotation operator by an E-species torsional-coordinate factor of the form e ± ni α . The resulting operator is capable of connecting the two components of a degenerate torsion-rotation E state. This has the effect of turning the hyperfine splitting pattern upside down for some nuclear-spin states, which leads to bottom-to-top and top-to-bottom hyperfine selection rules for some transitions, and thus to an explanation for the unexpectedly large observed hyperfine splittings. The constructed operator cannot contribute to hyperfine splittings in the A-species manifold because its matrix elements within the set of torsion-rotation A 1 and A 2 states are all zero. The theory developed here fits the observed large doublet splittings to a root-mean-square residual of less than 1 kHz and predicts unresolvable splittings for a number of transitions in which no doublet splitting was detected.

Description: In terms of the local bond-orientational order (LBOO) parameters, a cluster approach to analyze local structures of simple liquids was developed. In this approach, a cluster is defined as a combination of neighboring seeds having at least n b local-orientational bonds and their nearest neighbors, and a cluster ensemble is a collection of clusters with a specified n b and number of seeds n s . This cluster analysis was applied to investigate the microscopic structures of liquid Ga at ambient pressure (AP). The liquid structures studied were generated through ab initio molecular dynamics simulations. By scrutinizing the static structure factors (SSFs) of cluster ensembles with different combinations of n b and n s , we found that liquid Ga at AP contained two types of cluster structures, one characterized by sixfold orientational symmetry and the other showing fourfold orientational symmetry. The SSFs of cluster structures with sixfold orientational symmetry were akin to the SSF of a hard-sphere fluid. On the contrary, the SSFs of cluster structures showing fourfold orientational symmetry behaved similarly as the anomalous SSF of liquid Ga at AP, which is well known for exhibiting a high-q shoulder. The local structures of a highly LBOO cluster whose SSF displayed a high-q shoulder were found to be more similar to the structure of β-Ga than those of other solid phases of Ga. More generally, the cluster structures showing fourfold orientational symmetry have an inclination to resemble more to β -Ga.

Description: Resonant soft X-ray reflectivity at the carbon K edge, with linearly polarized light, was used to derive quantitative information of film morphology, molecular arrangement, and electronic orbital anisotropies of an ultrathin 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) film on Au(111). The experimental spectra were simulated by computing the propagation of the electromagnetic field in a trilayer system (vacuum/PTCDA/Au), where the organic film was treated as an anisotropic medium. Optical constants were derived from the calculated (through density functional theory) absorption cross sections of the single molecule along the three principal molecular axes. These were used to construct the dielectric tensor of the film, assuming the molecules to be lying flat with respect to the substrate and with a herringbone arrangement parallel to the substrate plane. Resonant soft X-ray reflectivity proved to be extremely sensitive to film thickness, down to the single molecular layer. The best agreement between simulation and experiment was found for a film of 1.6 nm, with flat laying configuration of the molecules. The high sensitivity to experimental geometries in terms of beam incidence and light polarization was also clarified through simulations. The optical anisotropies of the organic film were experimentally determined and through the comparison with calculations, it was possible to relate them to the orbital symmetry of the empty electronic states.

Description: An automated property optimization method was developed based on the ab initio O( N ) elongation (ELG) method and applied to the optimization of nonlinear optical (NLO) properties in DNA as a first test. The ELG method mimics a polymerization reaction on a computer, and the reaction terminal of a starting cluster is attacked by monomers sequentially to elongate the electronic structure of the system by solving in each step a limited space including the terminal (localized molecular orbitals at the terminal) and monomer. The ELG-finite field (ELG-FF) method for calculating (hyper-)polarizabilities was used as the engine program of the optimization method, and it was found to show linear scaling efficiency while maintaining high computational accuracy for a random sequenced DNA model. Furthermore, the self-consistent field convergence was significantly improved by using the ELG-FF method compared with a conventional method, and it can lead to more feasible NLO property values in the FF treatment. The automated optimization method successfully chose an appropriate base pair from four base pairs (A, T, G, and C) for each elongation step according to an evaluation function. From test optimizations for the first order hyper-polarizability (β) in DNA, a substantial difference was observed depending on optimization conditions between “choose-maximum” (choose a base pair giving the maximum β for each step) and “choose-minimum” (choose a base pair giving the minimum β). In contrast, there was an ambiguous difference between these conditions for optimizing the second order hyper-polarizability (γ) because of the small absolute value of γ and the limitation of numerical differential calculations in the FF method. It can be concluded that the ab initio level property optimization method introduced here can be an effective step towards an advanced computer aided material design method as long as the numerical limitation of the FF method is taken into account.

Description: We report an implementation of the molecular gradient using the divide-expand-consolidate resolution of the identity second-order Møller-Plesset perturbation theory (DEC-RI-MP2). The new DEC-RI-MP2 gradient method combines the precision control as well as the linear-scaling and massively parallel features of the DEC scheme with efficient evaluations of the gradient contributions using the RI approximation. We further demonstrate that the DEC-RI-MP2 gradient method is capable of calculating molecular gradients for very large molecular systems. A test set of supramolecular complexes containing up to 158 atoms and 1960 contracted basis functions has been employed to demonstrate the general applicability of the DEC-RI-MP2 method and to analyze the errors of the DEC approximation. Moreover, the test set contains molecules of complicated electronic structures and is thus deliberately chosen to stress test the DEC-RI-MP2 gradient implementation. Additionally, as a showcase example the full molecular gradient for insulin (787 atoms and 7604 contracted basis functions) has been evaluated.

Description: The background to this work was a prototype shadow sensor, which was designed for retro-fitting to an advanced LIGO (Laser Interferometer Gravitational wave Observatory) test-mass/mirror suspension, in which a 40 kg test-mass/mirror is suspended by four approximately 600 mm long by 0.4 mm diameter fused-silica suspension fibres. The shadow sensor comprised a LED source of Near InfraRed (NIR) radiation, and a “tall-thin” rectangular silicon photodiode detector, which together were to bracket the fibre under test. The photodiode was positioned so as to be sensitive (primarily) to transverse “Violin-Mode” vibrations of such a fibre, via the oscillatory movement of the shadow cast by the fibre, as this moved across the face of the detector. In this prototype shadow sensing system the photodiode was interfaced to a purpose-built transimpedance amplifier, this having both AC and DC outputs. A quasi-static calibration was made of the sensor’s DC responsivity, i.e., incremental rate of change of output voltage versus fibre position, by slowly scanning a fused-silica fibre sample transversely through the illuminating beam. The work reported here concerns the determination of the sensor’s more important AC (Violin-Mode) responsivity. Recognition of the correspondence between direct AC modulation of the source, and actual Violin-Mode signals, and of the transformative role of the AC / DC gain ratio for the amplifier, at any modulation frequency, f , resulted in the construction of the AC / DC calibration source described here. A method for determining in practice the transimpedance AC / DC gain ratio of the photodiode and amplifier, using this source, is illustrated by a specific numerical example, and the gain ratio for the prototype sensing system is reported over the frequency range 1 Hz–300 kHz. In fact, a maximum DC responsivity of 1.26 kV.m −1 was measured using the prototype photodiode sensor and amplifier discussed here. Therefore, the measured AC / DC transimpedance gain ratio of 922.5 for this sensor, at 500 Hz, translated into a maximum Violin-Mode ( AC ) responsivity of (1.16 ± 0.05) MV m −1 , at that frequency.

Description: A device is presented allowing for in situ investigation of chemically changing materials by means of X-ray imaging. A representative cork ablator sample, additionally instrumented with thermocouples, is encapsulated in an evacuated cell heating a sample surface with a heat flux of 230 kW/m 2 . The images show the sample surface and the in-depth progression of the char front dividing the char layer from the virgin material. Correlating the images to thermocouple data allows for the deduction of a reaction temperature. For the representative cork ablator investigated at the present conditions, the progression rate of the pyrolysis layer is determined to 0.0285 mm/s and pyrolysis temperature is 770 or 737 K, depending on the pre-existing conditions. It is found that the novel device is ideally suited for volume process imaging.

Description: In this communication, a novel optical technique has been proposed for the reconstruction of the shape of a Taylor bubble using measurements from multiple arrays of optical sensors. The deviation of an optical beam passing through the bubble depends on the contour of bubble surface. A theoretical model of the deviation of a beam during the traverse of a Taylor bubble through it has been developed. Using this model and the time history of the deviation captured by the sensor array, the bubble shape has been reconstructed. The reconstruction has been performed using an inverse algorithm based on Bayesian inference technique and Markov chain Monte Carlo sampling algorithm. The reconstructed nose shape has been compared with the true shape, extracted through image processing of high speed images. Finally, an error analysis has been performed to pinpoint the sources of the errors.

Description: Based on vibrational spectroscopy, coherent Raman Scattering (CRS) microscopy allows label-free imaging of biological and chemical samples with endogenous image contrast. Two-color, synchronized picosecond pulses are typically used for high spectral resolution imaging, which in turn constitutes a dramatic laser source challenge for CRS microscopy. Recently, synchronized time-lens source, inspired from ultrafast optical signal processing, has emerged as a promising laser source solution and has found application in various modalities of CRS microscopy. Time-lens is based on space-time analogy, which uses a “lens” in the time domain to compress long optical pulses or even continuous waves to ultrashort pulses, mimicking a lens in the space domain. Phase and intensity modulators driven with electrical signals are used in the time-lens source for picosecond pulse generation. As a result, the time-lens source is highly versatile and naturally compatible with modulation capabilities. More importantly, if the electrical signals used to drive the time-lens source are derived from other laser sources, such as mode-locked lasers, then synchronization between them can be realized, underlying the physics of a synchronized time-lens source. In this paper, we review recent progress on the basic principle, design of the synchronized time-lens source, and its applications to CRS microscopy of both biological and chemical samples.

Description: In this paper, a new double micropipettes configuration mode of scanning ion conductance microscopy (SICM) is presented to better overcome ionic current drift and further improve the performance of SICM, which is based on a balance bridge circuit. The article verifies the feasibility of this new configuration mode from theoretical and experimental analyses, respectively, and compares the quality of scanning images in the conventional single micropipette configuration mode and the new double micropipettes configuration mode. The experimental results show that the double micropipettes configuration mode of SICM has better effect on restraining ionic current drift and better performance of imaging. Therefore, this article not only proposes a new direction of overcoming the ionic current drift but also develops a new method of SICM stable imaging.

Description: A new imaging algorithm is proposed to capture the kinematics of flexible, thin, light structures including frequencies and motion amplitudes for real time analysis. The studied case is a thin flexible beam that is preset at different angles of attack in a wind tunnel. As the angle of attack is increased beyond a critical value, the beam was observed to undergo a static deflection that is ensued by limit cycle oscillations. Imaging analysis of the beam vibrations shows that the motion consists of a superposition of the bending and torsion modes. The proposed algorithm was able to capture the oscillation amplitudes as well as the frequencies of both bending and torsion modes. The analysis results are validated through comparison with measurements from a piezoelectric sensor that is attached to the beam at its root.

Description: A thermal dissociation cavity attenuated phase shift spectroscopy (TD-CAPS) instrument was developed for measuring total peroxy nitrates (PNs) and organic nitrates (ONs) concentrations in the clean atmosphere. This instrument is easy to operate and can be applied to continuous measurement of PNs and ONs. A continuously measurable system is convenient to perform observations, especially in remote areas. Three lines (NO 2 , PNs, and ONs lines) were used for thermal dissociation. The NO 2 line contains a quartz tube that is not heated, while the PN and ON lines contain quartz tubes that are heated at 433 K and 633 K, respectively. The concentrations of NO 2 , NO 2 + PNs, and NO 2 + PNs + ONs can be obtained from the NO 2 , PN, and ON lines, respectively. The lower limit values of the detection limit (3σ) for PNs and ONs were estimated to be 21 parts per trillion by volume with an integration time of 2 min. PNs were selectively thermally decomposed in the PNs line and formed NO 2 quantitatively. In the ONs line, both PNs and ONs were thermally decomposed to produce NO 2 quantitatively, but partial decomposition of HNO 3 at 633 K interfered with the ONs measurement. Therefore, a HNO 3 scrubber is required before the ONs line. Continuous observations were conducted with the TD-CAPS instrument in a remote area, and the instrument performed well for obtaining PNs and ONs concentrations.

Description: A novel diamond anvil cell suitable for electrical transport measurements under high pressure has been developed. A boron-doped metallic diamond film was deposited as an electrode on a nano-polycrystalline diamond anvil using a microwave plasma-assisted chemical vapor deposition technique combined with electron beam lithography. The maximum pressure that can be achieved by this assembly is above 30 GPa. We report electrical transport measurements of Pb up to 8 GPa. The boron-doped metallic diamond electrodes showed no signs of degradation after repeated compression.

Description: Optical birefringence imaging systems demonstrate a high potential for comprehensively investigating various phase transitions. To completely demonstrate such abilities, the temperature dependence of birefringence (Δ n ) was measured in Δ n ≃ 0 materials (i.e., cubic crystals with imperfect crystallization) via a background subtraction method. As a result, highly accurate birefringence imaging at 384 × 288 pixels was obtained using phase transition processes as well as varying temperatures visually characterized by the spatial distribution of not only the retardance level but also the optical fast-axis azimuth.

Description: A free space measurement method, which consists of two horn antennas, a network analyzer, two frequency extenders, and a sample holder, is used to measure transmission ( S 21 ) coefficients in 75-110 GHz (W-Band) frequency range. Singular spectrum analysis method is presented to eliminate the error and noise of raw S 21 data after calibration and measurement processes. The proposed model can be applied easily to remove the repeated calibration process for each sample measurement. Hence, smooth, reliable, and accurate data are obtained to determine the dielectric properties of materials. In addition, the dielectric constant of materials (paper, polyvinylchloride-PVC, Ultralam® 3850HT, and glass) is calculated by thin sheet approximation and Newton-Raphson extracting techniques using a filtered S 21 transmission parameter.

Description: An electron density diagnostic (≥10 10 cm −3 ) capable of high temporal (ms) and spatial (mm) resolution is currently under development at Oak Ridge National Laboratory. The diagnostic is based on measuring the Stark broadened, Doppler-free spectral line profile of the n = 6–2 hydrogen Balmer series transition. The profile is then fit to a fully quantum mechanical model including the appropriate electric and magnetic field operators. The quasi-static approach used to calculate the Doppler-free spectral line profile is outlined here and the results from the model are presented for H-δ spectra for electron densities of 10 10 –10 13 cm −3 . The profile shows complex behavior due to the interaction between the magnetic substates of the atom.

Description: This paper presents the first design and experimental demonstration of an ultrahigh frequency complete phononic crystal (PnC) bandgap aluminum nitride (AlN)/air structure operating in the GHz range. A complete phononic bandgap of this design is used to efficiently and simultaneously confine elastic vibrations in a resonator. The PnC structure is fabricated by etching a square array of air holes in an AlN slab. The fabricated PnC resonator resonates at 1.117 GHz, which corresponds to an out-of-plane mode. The measured bandgap and resonance frequencies are in very good agreement with the eigen-frequency and frequency-domain finite element analyses. As a result, a quality factor/volume of 7.6 × 10 17 /m 3 for the confined resonance mode was obtained that is the largest value reported for this type of PnC resonator to date. These results are an important step forward in achieving possible applications of PnCs for RF communication and signal processing with smaller dimensions.

Description: In this work, titanium dioxide nanotubes were prepared by using titanium foils via electrochemical anodization in ethylene glycol solutions containing different amounts of water and fluoride in the ranges of 1%–3% and 0.15%–0.5%, respectively, to determine their effects on morphology, optical, and crystalline structure properties. Annealing processes were performed on all samples in the range between 273 and 723 K. Morphology and structure properties of the samples were studied by scanning electron microscopy, X-ray diffraction (XRD), and transmission electron microscopy. Titanium dioxide (TiO 2 ) nanotubes, through anodization method, are strongly influenced by conditions, like fluoride concentration and applied voltages. Tube lengths between 2 and 7  μ m were obtained, exhibiting different diameters and wall thicknesses. When alternating voltage was applied, the outer surface of the nanotubes exhibited evenly spaced ring-shaped regions, while smooth tubes were observed when constant voltage was applied. Reflection peaks, corresponding to Brookite, Anatase, and Rutile, of TiO 2 phases, were observed from the XRD pattern. These phases were corroborated via μXRD measurements, and the Ti 3 O 5 phase was also observed in detail. Absorption coefficient (α), optical band gap (Eg), and extinction coefficient (ε) of TiO 2 nanotubes were calculated by transmittance spectra in the UV–Vis range. Strong absorption was noted in the UV region from reflectance and absorbance measurements. A correlation between synthesis parameters and physical properties is presented.

Description: Hydrodynamic interactions with confining boundaries often lead to drastic changes in the diffusive behaviour of microparticles in suspensions. For axially symmetric particles, earlier numerical studies have suggested a simple form of the near-wall diffusion matrix which depends on the distance and orientation of the particle with respect to the wall, which is usually calculated numerically. In this work, we derive explicit analytical formulae for the dominant correction to the bulk diffusion tensor of an axially symmetric colloidal particle due to the presence of a nearby no-slip wall. The relative correction scales as powers of inverse wall-particle distance and its angular structure is represented by simple functions in sines and cosines of the particle’s inclination angle to the wall. We analyse the correction for translational and rotational motion, as well as the translation-rotation coupling. Our findings provide a simple approximation to the anisotropic diffusion tensor near a wall, which completes and corrects relations known from earlier numerical and theoretical findings.

Description: This manuscript presents the second, consistent density functional in the QTP (Quantum Theory Project) family, that is, the CAM-QTP(01). It is a new range-separated exchange-correlation functional in which the non-local exchange contribution is 100% at large separation. It follows the same basic principles of this family that the Kohn-Sham eigenvalues of the occupied orbitals approximately equal the vertical ionization energies, which is not fulfilled by most of the traditional density functional methods. This new CAM-QTP(01) functional significantly improves the accuracy of the vertical excitation energies especially for the Rydberg states in the test set. It also reproduces many other properties such as geometries, reaction barrier heights, and atomization energies.

Description: Core excitation energies are computed with time-dependent density functional theory (TD-DFT) using the ionization energy corrected exchange and correlation potential QTP(0,0). QTP(0,0) provides C, N, and O K-edge spectra to about an electron volt. A mean absolute error (MAE) of 0.77 and a maximum error of 2.6 eV is observed for QTP(0,0) for many small molecules. TD-DFT based on QTP (0,0) is then used to describe the core-excitation spectra of the 22 amino acids. TD-DFT with conventional functionals greatly underestimates core excitation energies, largely due to the significant error in the Kohn-Sham occupied eigenvalues. To the contrary, the ionization energy corrected potential, QTP(0,0), provides excellent approximations (MAE of 0.53 eV) for core ionization energies as eigenvalues of the Kohn-Sham equations. As a consequence, core excitation energies are accurately described with QTP(0,0), as are the core ionization energies important in X-ray photoionization spectra or electron spectroscopy for chemical analysis.

Description: Details of crystallization processes of a polymer at the crystallization temperature T c from its melt kept initially at the melt temperature T m depend profoundly on the nature of the initial melt state and often are accompanied by memory effects. This phenomenon is in contrast to small molecular systems where the supercooling ( T m 0 − T c ), with T m 0 being the equilibrium melting temperature, and not ( T m − T c ), determines the nature of crystallization. In addressing this five-decade old puzzle of melt-memory in polymer crystallization, we present a theory to describe melt-memory effects, by invoking an intermediate inhomogeneous melt state in the pathway between the melt and crystalline states. Using newly introduced dissolution temperature T 1 0 for the inhomogeneous melt state and the transition temperature T t 0 for the transition between the inhomogeneous melt and crystalline states, analytical formulas are derived for the nucleation rate as a function of the melt temperature. The theory is general to address different kinds of melt-memory effects depending on whether T m is higher or lower than T m 0 . The derived results are in qualitative agreement with known experimental data, while making predictions for further experiments on melt-memory.

Description: Long-lived spin coherence and rotationally ordered radical pairs have previously been identified as key requirements for the radical pair mechanism of the avian magnetic compass sense. Both criteria are hard to meet in a biological environment, where thermal motion of the radicals creates dynamic disorder and drives efficient spin relaxation. This has long been cited as a major stumbling block of the radical pair hypothesis. Here we combine Redfield relaxation theory with analytical solutions to a rotational diffusion equation to assess the impact of restricted rotational motion of the radicals on the operation of the compass. The effects of such motions are first investigated generally in small, model systems and are then critically examined in the magnetically sensitive flavin-tryptophan radical pair that is formed photochemically in the proposed magnetoreceptor protein, cryptochrome. We conclude that relaxation is slowest when rotational motion of the radicals within the protein is fast and highly constrained; that in a regime of slow relaxation, the motional averaging of hyperfine interactions has the potential to improve the sensitivity of the compass; and that consideration of motional effects can significantly alter the design criteria for an optimal compass. In addition, we demonstrate that motion of the flavin radical is likely to be compatible with its role as a component of a functioning radical-pair compass, whereas the motion of the tryptophan radical is less ideal, unless it is particularly fast.

Description: Bottom-up multiscale techniques are frequently used to develop coarse-grained (CG) models for simulations at extended length and time scales but are often limited by a compromise between computational efficiency and accuracy. The conventional approach to CG nonbonded interactions uses pair potentials which, while computationally efficient, can neglect the inherently multibody contributions of the local environment of a site to its energy, due to degrees of freedom that were coarse-grained out. This effect often causes the CG potential to depend strongly on the overall system density, composition, or other properties, which limits its transferability to states other than the one at which it was parameterized. Here, we propose to incorporate multibody effects into CG potentials through additional nonbonded terms, beyond pair interactions, that depend in a mean-field manner on local densities of different atomic species. This approach is analogous to embedded atom and bond-order models that seek to capture multibody electronic effects in metallic systems. We show that the relative entropy coarse-graining framework offers a systematic route to parameterizing such local density potentials. We then characterize this approach in the development of implicit solvation strategies for interactions between model hydrophobes in an aqueous environment.

Description: C-2U is a high-confinement, advanced beam driven field-reversed configuration plasma experiment which sustains the configuration for 〉5 ms, in excess of typical MHD and fast particle instability times, as well as fast particle slowing down times. Fast particle dynamics are critical to C-2U performance and several diagnostics have been deployed to characterize the fast particle population, including neutron and proton detectors. To increase our understanding of fast particle behavior and supplement existing diagnostics, an E ∥ B neutral particle analyzer was installed, which simultaneously measures H 0 and D 0 flux with large dynamic range and high energy resolution. Here we report the commissioning of the E ∥ B analyzer, confirm the instrument has energy resolution Δ E / E ≲ 0 . 1 and a dynamic range E max / E min ∼ 30 , and present measurements of initial testing on C-2U.

Description: Compact pulsed power system based on compact Marx generator is widely used in terms of drive resistance and capacitive loads. This system usually adopts high performance components such as high energy density capacitors, compact switches, and integrated structure. Traditional compact Marx generator can only output double-exponential pulse profile. In this paper a compact, low-impedance Marx module which can output rectangular pulse profile is design and tested. This module has multiple circuits of different discharge frequencies in parallel to generate quasi-rectangular pulse. Discharge characteristic of an ideal module with infinite branches is calculated theoretically. A module with two branches has been designed and tested. Test results show that the impedance of the module is 1.2 Ω. When charging voltage is 100.6 kV and load resistance is 1 Ω, the peak output pulse is 45.2 kV voltage, the peak power is about 2 GW, the pulse width is about 130 ns, and the rise time is about 35 ns. The energy density and power density of the module are 15 kJ/m 3 and 140 GW/m 3 , respectively.

Description: An optical flux sensor, based on the fluorescence properties of materials and nanoparticles, has been developed to control the deposition rate in thin film deposition systems. Using a simple diode laser and a photomultiplier tube with a light filter, we report the detection of gallium atoms and CdSe-ZnS quantum dots. This setup has a high sensitivity and reproducibility.

Description: Similar to electromagnetism, described by the Maxwell equations, the physics of magnetoelectric (ME) phenomena deals with the fundamental problem of the relationship between electric and magnetic fields. Despite a formal resemblance between the two notions, they concern effects of different natures. In general, ME-coupling effects manifest in numerous macroscopic phenomena in solids with space and time symmetry breakings. Recently, it was shown that the near fields in the proximity of a small ferrite particle with magnetic-dipolar-mode (MDM) oscillations have the space and time symmetry breakings and the topological properties of these fields are different from the topological properties of the free-space electromagnetic fields. Such MDM-originated fields—called magnetoelectric (ME) fields—carry both spin and orbital angular momenta. They are characterized by power-flow vortices and non-zero helicity. In this paper, we report on observation of the topological ME effects in far-field microwave radiation based on a small microwave antenna with a MDM ferrite resonator. We show that the microwave far-field radiation can be manifested with a torsion structure where an angle between the electric and magnetic field vectors varies. We discuss the question on observation of the regions of localized ME energy in far-field microwave radiation.

Description: The epitaxial integration of functional oxides with wide band gap semiconductors offers the possibility of new material systems for electronics and energy conversion applications. We use first principles to consider an epitaxial interface between the correlated metal oxide SrRuO 3 and the wide band gap semiconductor TiO 2 , and assess energy level alignment, interfacial chemistry, and interfacial dipole formation. Due to the ferromagnetic, half-metallic character of SrRuO 3 , according to which only one spin is present at the Fermi level, we demonstrate the existence of a spin dependent band alignment across the interface. For two different terminations of SrRuO 3 , the interface is found to be rectifying with a Schottky barrier of ≈1.3–1.6 eV, in good agreement with experiment. In the minority spin, SrRuO 3 exhibits a Schottky barrier alignment with TiO 2 and our calculated Schottky barrier height is in excellent agreement with previous experimental measurements. For majority spin carriers, we find that SrRuO 3 recovers its exchange splitting gap and bulk-like properties within a few monolayers of the interface. These results demonstrate a possible approach to achieve spin-dependent transport across a heteroepitaxial interface between a functional oxide material and a conventional wide band gap semiconductor.

Description: The aim of this work is to analyze in more depth a model of particle deposition by characterizing different parameters such as profile density, bonds and perimeter, and substrate coverage, all being involved in the description of deposits as bulk. Thus, this study is an extension of a previous work on non-equilibrium interface-growth systems where two different interface-growth models, called Standard Adherence Rule Model and Potential Adherence Rule Model, were characterized. In this work, bulk characterization is implemented for the complete range of Peclet numbers. The zones of density profile (Near-Wall, Plateau, and Active-Growth) are studied by proposing an adjustment for each of them and determining the full-setting density profile depending on the Peclet number. The density profiles are compared with other one- and two-stage models. Furthermore, an algorithm is proposed to calculate the number of bonds of the particles and the perimeter that a substrate forms over time. Finally, to analyze the coating, its temporal behavior is adjusted to an exponential function by comparing the results with those found for Random Sequential Adsorption models which describe systems like colloidal particles on solid substrates, adsorption of proteins at mineral surfaces, or oxidation of one-dimensional polymer chains.

Description: The recently discovered hexagonal ABC -type hyperferroelectrics, in which the polarization persists in the presence of the depolarization filed, exhibit a variety of intriguing and potentially useful properties [Garrity et al ., Phys. Rev. Lett. 112 , 127601 (2014)]. For the existing prototype of LiBeSb, we present detailed first-principles calculations concerning the lattice dynamics, electronic structure, and optical properties. An unstable longitudinal optic mode in the high-symmetry structure and a large polarization of 0.5 C/m 2 in the polar phase are reported, including the remarkable dependence of Born effective charges on structural distortion. Using the HSE06 hybrid functional, we predict that LiBeSb has a small band-gap of 1.5 eV and shows dominant asymmetric covalent bonding character. Importantly, we find that there are remarkable absorptions in the whole visible spectrum. These features, combined with the enhanced carrier mobility, make LiBeSb as well as the whole family of hexagonal ABC -type hyperferroelectrics as promising candidates for ferroelectric photovoltaic materials with large bulk photovoltaic effect in the visible spectrum.

Description: We combine classical nucleation theory with superharmonic focusing to predict necessary pressures to induce nucleation in acoustic droplet vaporization. We show that linear acoustics is a valid approximation to leading order when particle displacements in the sound field are small relative to the radius of the droplet. This is done by perturbation analysis of an axisymmetric compressible inviscid flow about a droplet with small surface perturbations relative to the mean radius subjected to an incoming ultrasonic wave. The necessary nucleation pressure threshold inside the droplet is calculated to be −9.33 ± 0.30 MPa for typical experimental parameters by employing results from classical homogeneous nucleation theory . As a result, we are able to predict if a given incident pressure waveform will induce nucleation.

Description: Resonant dipolar relaxation in poly( ε -caprolactone) (PCL) is reported using thermally stimulated discharge current spectroscopy. PCL is a bio-medically known shape memory polymer having a well defined γ , β , α , and α ′ relaxations, respectively, centered around 125 K, 170 K, 220 K, and 270 K as seen by the measurements. By employing a new protocol variable poling temperature at constant freezing temperature, resonant dipolar relaxation in PCL could be induced, especially in the vicinity of α relaxation. Such a protocol is useful in de-convoluting the features in a more meaningful fashion. By an analysis of activation process, we could show a clear contrast enhancement of the dynamics of the participating dipoles by means of a minimum in the activation energies situated around the glass transition region. The relevant parameters of interest such as activation energies and relaxation times are estimated and discussed.

Description: We report the growth of thin films of the mixed valence compound YbAl 3 on MgO using molecular-beam epitaxy. Employing an aluminum buffer layer, epitaxial (001) films can be grown with sub-nm surface roughness. Using x-ray diffraction, in situ low-energy electron diffraction, and aberration-corrected scanning transmission electron microscopy, we establish that the films are ordered in the bulk as well as at the surface. Our films show a coherence temperature of 37 K, comparable to that reported for bulk single crystals. Photoelectron spectroscopy reveals contributions from both f 13 and f 12 final states establishing that YbAl 3 is a mixed valence compound and shows the presence of a Kondo Resonance peak near the Fermi-level.

Description: In this work, a new rigid-nonpolarizable model of methanol is proposed. The model has three sites, located at the same positions as those used in the OPLS model previously proposed by Jorgensen [J. Phys. Chem. 90 , 1276 (1986)]. However, partial charges and the values of the Lennard-Jones parameters were modified by fitting to an adequately selected set of target properties including solid-fluid experimental data. The new model was denoted as OPLS/2016. The overall performance of this model was evaluated and compared to that obtained with other popular models of methanol using a similar test to that recently proposed for water models. In the test, a certain numerical score is given to each model. It was found that the OPLS/2016 obtained the highest score (7.4 of a maximum of 10) followed by L1 (6.6), L2 (6.4), OPLS (5.8), and H1 (3.5) models. The improvement of OPLS/2016 with respect to L1 and L2 is mainly due to an improvement in the description of fluid-solid equilibria (the melting point is only 14 K higher than the experimental value). In addition, it was found that no methanol model was able to reproduce the static dielectric constant and the isobaric heat capacity, whereas the better global performance was found for models that reproduce the vaporization enthalpy once the so-called polarization term is included. Similar conclusions were suggested previously in the analysis of water models and are confirmed here for methanol.

Description: We investigate the link between dynamic localization, characterized by the Debye–Waller factor, 〈 u 2 〉, and solute self-diffusivity, D , in a polymer system using atomistic molecular dynamics simulations and vapor sorption experiments. We find a linear relationship between ln D and 1/〈 u 2 〉 over more than four decades of D , encompassing most of the glass formation regime. The observed linearity is consistent with the Langevin dynamics in a periodically varying potential field and may offer a means to rapidly assess diffusion based on the characterization of dynamic localization.

Description: An improved method for characterizing the magnetic anisotropy of films with cubic symmetry is described and is applied to an yttrium iron garnet (111) film. Analysis of the ferromagnetic resonance (FMR) spectra performed both in-plane and out-of-plane from 0.7 to 8 GHz yielded the magnetic anisotropy constants as well as the saturation magnetization. The field at which FMR is observed turns out to be quite sensitive to anisotropy constants (by more than a factor ten) in the low frequency (

Description: It is general wisdom that the pair potential of charged colloids in a liquid may be closely approximated by a Yukawa interaction, as predicted by the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. We experimentally determine the effective forces in a binary mixture of like-charged particles, of species 1 and 2, with blinking optical tweezers. The measured forces are consistent with a Yukawa pair potential but the (12) cross-interaction is not equal to the geometric mean of the (11) and (22) like-interactions, as expected from DLVO. The deviation is a function of the electrostatic screening length and the size ratio, with the cross-interaction measured being consistently weaker than DLVO predictions. The corresponding non-additivity parameter is negative and grows in magnitude with increased size asymmetry.

Description: Radiochromic films (RCF) are commonly used in dosimetry for a wide range of radiation sources (electrons, protons, and photons) for medical, industrial, and scientific applications. They are multi-layered, which includes plastic substrate layers and sensitive layers that incorporate a radiation-sensitive dye. Quantitative dose can be retrieved by digitizing the film, provided that a prior calibration exists. Here, to calibrate the newly developed EBT3 and HDv2 RCFs from Gafchromic™, we used the Stanford Medical LINAC to deposit in the films various doses of 10 MeV photons, and by scanning the films using three independent EPSON Precision 2450 scanners, three independent EPSON V750 scanners, and two independent EPSON 11000XL scanners. The films were scanned in separate RGB channels, as well as in black and white, and film orientation was varied. We found that the green channel of the RGB scan and the grayscale channel are in fact quite consistent over the different models of the scanner, although this comes at the cost of a reduction in sensitivity (by a factor ∼2.5 compared to the red channel). To allow any user to extend the absolute calibration reported here to any other scanner, we furthermore provide a calibration curve of the EPSON 2450 scanner based on absolutely calibrated, commercially available, optical density filters.

Description: The anode pulse of a photomultiplier tube (PMT) coupled with a scintillator is used for pulse shape discrimination (PSD) analysis. We have developed a novel emulation technique for the PMT anode pulse based on optical photon transport and a PMT response function. The photon transport was calculated using Geant4 Monte Carlo code and the response function with a BC408 organic scintillator. The obtained percentage RMS value of the difference between the measured and simulated pulse with suitable scintillation properties using GSO:Ce (0.4, 1.0, 1.5 mol%), LaBr 3 :Ce and BGO scintillators were 2.41%, 2.58%, 2.16%, 2.01%, and 3.32%, respectively. The proposed technique demonstrates high reproducibility of the measured pulse and can be applied to simulation studies of various radiation measurements.

Description: In this study, fullerene like carbon (FL-C) is introduced in hydrogenated amorphous carbon (a-C:H) film by employing a direct current plasma enhanced chemical vapor deposition. The film has a low friction and wear, such as 0.011 and 2.3 × 10 −9 mm 3 /N m in the N 2 , and 0.014 and 8.4 × 10 −8 mm 3 /N m in the humid air, and high hardness and elasticity (25.8 GPa and 83.1%), to make further engineering applications in practice. It has several nanometers ordered domains consisting of less frequently cross-linked graphitic sheet stacks. We provide new evidences for understanding the reported Raman fit model involving four vibrational frequencies from five, six, and seven C-atom rings of FL-C structures, and discuss the structure evolution before or after friction according to the change in the 1200 cm −1 Raman band intensity caused by five- and seven-carbon rings. Friction inevitably facilitates the transformation of carbon into FL-C nanostructures, namely, the ultra low friction comes from both such structures within the carbon film and the sliding induced at friction interface.

Description: It was shown that drilling of multi-layered target placed in the air by tightly focused femtosecond laser radiation with high fluence (up to 1000 J/cm 2 ) can be monitored online using plasma-induced X-ray emission and second harmonic of incident laser radiation. The technique based on X-rays registration is appeared to be more flexible than the method based on detection of second harmonic since its accuracy depends crucially on the target type. We demonstrated that the X-ray signal clearly indicates the transition from one layer to another during the microdrilling of targets consisting of 2–4 layers of titanium foil when a laser beam is focused beneath the target surface at a depth comparable to the layer thickness. The diagnostics of microchannel production in the chicken eggshell was performed for the first time. It was found that the presence of albumen beneath the shell accounts for longtime generation of X-ray pulses.

Description: This work reports on the effects of a deep high-dose hydrogen ion implant on damage accumulation, defect retention, and silver diffusion in silver implanted ZnO crystals. Single-crystal ZnO samples were implanted with Ag ions in a region ∼150 nm within the surface, and some of these samples were additionally implanted with hydrogen ions to a dose of 2 × 10 16  cm −2 , close to the depth ∼250 nm. Rutherford backscattering/ion channeling measurements show that crystal damage caused by Ag ion implantation and the amount of defects retained in the near surface region following post-implantation annealing were found to diminish in the case with the H implantation. On the other hand, the additional H ion implantation resulted in a reduction of substitutional Ag atoms upon post-implantation annealing. Furthermore, the presence of H also modified the diffusion properties of Ag atoms in ZnO. We discuss these findings in the context of the effects of nano-cavities on formation and annihilation of point defects as well as on impurity diffusion and trapping in ZnO crystals.

Description: The formation and evolution of spin wave band gaps in the transmission spectrum of a magnonic crystal have been studied. A time and space resolved magneto inductive probing system has been used to map the spin wave propagation and evolution in a geometrically structured yttrium iron garnet film. Experiments have been carried out using (1) a chemically etched magnonic crystal supporting the propagation of magnetostatic surface spin waves, (2) a short microwave pulsed excitation of the spin waves, and (3) direct spin wave detection using a movable magneto inductive probe connected to a synchronized fast oscilloscope. The results show that the periodic structure not only modifies the spectra of the transmitted spin waves but also influences the distribution of the spin wave energy inside the magnonic crystal as a function of the position and the transmitted frequency. These results comprise an experimental confirmation of Bloch′s theorem in a spin wave system and demonstrate good agreement with theoretical observations in analogue phononic and photonic systems. Theoretical prediction of the structured transmission spectra is achieved using a simple model based on microwave transmission lines theory. Here, a spin wave system illustrates in detail the evolution of a much more general physical concept: the band gap.

Description: The 8-band k · p parameters which include the direct band coupling between the conduction and the valence bands are derived and used to model optical intersubband transitions in Ge quantum well heterostructure material grown on Si substrates. Whilst for Si rich quantum wells the coupling between the conduction bands and valence bands is not important for accurate modelling, the present work demonstrates that the inclusion of such coupling is essential to accurately determine intersubband transitions between hole states in Ge and Ge-rich Si 1− x Ge x quantum wells. This is due to the direct bandgap being far smaller in energy in Ge compared to Si. Compositional bowing parameters for a range of the key modelling input parameters required for Ge/SiGe heterostructures, including the Kane matrix elements, the effective mass of the Γ 2 ′ conduction band, and the Dresselhaus parameters for both 6- and 8-band k · p modelling, have been determined. These have been used to understand valence band intersubband transitions in a range of Ge quantum well intersubband photodetector devices in the mid-infrared wavelength range.

Description: Rare-earth orthoniobates constitute a class of materials that has been exploited due to their interesting physical properties depending on the lanthanide element. Besides paramagnetism, ferroelasticity, and negative compressibility, these materials are known by their interesting optical properties and mixed types of conduction processes (protonic, ionic, and electronic). In this work, two types of SmNbO 4 samples were studied: polycrystalline samples, prepared by a sol-gel route using the Pechini method, and single crystalline fibres grown by the Laser Floating Zone technique. These samples were structurally characterized based on powder and single-crystal X-ray diffraction studies. A metastable tetragonal phase, stabilized by grain size, was identified in the synthesized powders. After a sintering process of such powders, a single monoclinic phase was obtained. Complementarily, scanning electron microscopy and Raman spectroscopy analyses were performed to these samples. Photoluminescence and photoluminescence excitation spectroscopic studies allowed identifying more than one optically active centre of the trivalent samarium ion in the analysed material. Impedance spectroscopy measurements have shown a large variation of the ac conductivity as a function of temperature, assigned to a protonic conduction and to native ionic conduction mechanisms.

Description: A series of polycrystalline YMn 1−x Ru x O 3 (0 ≤ x ≤ 0.2) samples were prepared by traditional solid-state reaction method. Effects of doping on the microstructures and magnetic properties were investigated. Microstructural results reveal that samples crystallize in a single hexagonal structure with P 6 3 cm group for x ≤ 0.1. Lattice parameters a, c, and unit-cell volume of YMn 1−x Ru x O 3 are found to increase with doping content, which are ascribed to the larger radius of Ru 3+ than that of Mn 3+ . Weak ferromagnetism is found and is enhanced with increasing doping concentration x. The bond angles of Mn-O3-Mn and Mn-O4-Mn are changed in the opposite trends, which break the Mn-Mn exchange interaction, thus the antiferromagnetic ordering. The MnO 5 bipyramid is found to be relieved and the trimerization of Mn ions is weakened. These structural modifications result in the increase of weak ferromagnetism ordering in samples.

Description: To increase the thermoelectric efficiency and reduce the thermal fatigue upon cyclic heat loading, alloying of amorphous NbO 2 with all 3d and 5d transition metals has systematically been investigated using density functional theory. It was found that Ta fulfills the key design criteria, namely, enhancement of the Seebeck coefficient and positive Cauchy pressure (ductility gauge). These quantum mechanical predictions were validated by assessing the thermoelectric and elastic properties on combinatorial thin films, which is a high-throughput approach. The maximum power factor is 2813  μ W m −1  K −2 for the Ta/Nb ratio of 0.25, which is a hundredfold increment compared to pure NbO 2 and exceeds many oxide thermoelectrics. Based on the elasticity measurements, the consistency between theory and experiment for the Cauchy pressure was attained within 2%. On the basis of the electronic structure analysis, these configurations can be perceived as metallic, which is consistent with low electrical resistivity and ductile behavior. Furthermore, a pronounced quantum confinement effect occurs, which is identified as the physical origin for the Seebeck coefficient enhancement.

Description: We investigated the optical properties of wurtzite (WZ) GaP nanowires by performing photoluminescence (PL) and time-resolved PL measurements in the temperature range from 4 K to 300 K, together with atom probe tomography to identify residual impurities in the nanowires. At low temperature, the WZ GaP luminescence shows donor-acceptor pair emission at 2.115 eV and 2.088 eV, and Burstein-Moss band-filling continuum between 2.180 and 2.253 eV, resulting in a direct band gap above 2.170 eV. Sharp exciton α-β-γ lines are observed at 2.140–2.164–2.252 eV, respectively, showing clear differences in lifetime, presence of phonon replicas, and temperature-dependence. The excitonic nature of those peaks is critically discussed, leading to a direct band gap of ∼2.190 eV and to a resonant state associated with the γ-line ∼80 meV above the Γ 8C conduction band edge.

Description: Quite recently, the magnon Hall effect of spin excitations has been observed experimentally on the kagome and pyrochlore lattices. The thermal Hall conductivity κ xy changes sign as a function of magnetic field or temperature on the kagome lattice, and κ xy changes sign upon reversing the sign of the magnetic field on the pyrochlore lattice. Motivated by these recent exciting experimental observations, we theoretically propose a simple realization of the magnon Hall effect in a two-band model on the honeycomb lattice. The magnon Hall effect of spin excitations arises in the usual way via the breaking of inversion symmetry of the lattice, however, by a next-nearest-neighbour Dzyaloshinsky-Moriya interaction. We find that κ xy has a fixed sign for all parameter regimes considered. These results are in contrast to the Lieb, kagome, and pyrochlore lattices. We further show that the low-temperature dependence on the magnon Hall conductivity follows a T 2 law, as opposed to the kagome and pyrochlore lattices. These results suggest an experimental procedure to measure thermal Hall conductivity within a class of 2D honeycomb quantum magnets and ultracold atoms trapped in a honeycomb optical lattice.

Description: The associative and dissociative adsorption of water molecules at low-coverage situations on rutile TiO 2 (110) surface with step defects was investigated by the density functional theory calculations. Structural optimization of the hydroxylated/hydrated configurations at step edges along the 1 1 ̄ 1 crystal directions and the dynamic process of water dissociation were discussed to get a better description of the water/TiO 2 interface. Our results indicate that steps on the TiO 2 (110) surface could be an active site for water dissociation. The results of geometry optimization suggest that the stability of hydroxylated configuration is largely dependent on the locations of the H species and the recombination of water molecules from hydroxyls is observed in the fully hydroxylated condition. However, these hydroxyls can be stabilized by the associatively absorbed water nearby by forming competitive intermolecular hydrogen bonds. The dynamics of water dissociation and hydrogen diffusion were studied by the first principles molecular dynamics simulation and our results suggest that the hydrogen released by water dissociation can be transferred among the adsorbates, such as the unsaturated oxygen atoms–H 2 O–hydroxyl (TiO–H 2 O–OH) complex at step edges, or gradually diffuses to the bulk water system in the form of hydronium (H 3 O + ) at higher water coverage.

Description: A series of CH stretch modes in phenyl radical (C 6 H 5 ) has been investigated via high resolution infrared spectroscopy at sub-Doppler resolution (∼60 MHz) in a supersonic discharge slit jet expansion. Two fundamental vibrations of a 1 symmetry, ν 1 and ν 2 , are observed and rotationally analyzed for the first time, corresponding to in-phase and out-of-phase symmetric CH stretch excitation at the ortho/meta/para and ortho/para C atoms with respect to the radical center. The ν 1 and ν 2 band origins are determined to be 3073.968 50(8) cm −1 and 3062.264 80(7) cm −1 , respectively, which both agree within 5 cm −1 with theoretical anharmonic scaling predictions based on density functional B3LYP/6-311g++(3df,3dp) calculations. Integrated band strengths for each of the CH stretch bands are analyzed, with the relative intensities agreeing remarkably well with theoretical predictions. Frequency comparison with previous low resolution Ar-matrix spectroscopy [A. V. Friderichsen et al. , J. Am. Chem. Soc. 123 , 1977 (2001)] reveals a nearly uniform Δν ≈ + 10-12 cm −1 blue shift between gas phase and Ar matrix values for ν 1 and ν 2 . This differs substantially from the much smaller red shift (Δν ≈ − 1 cm −1 ) reported for the ν 19 mode, and suggests a simple physical model in terms of vibrational mode symmetry and crowding due to the matrix environment. Finally, the infrared phenyl spectra are well described by a simple asymmetric rigid rotor Hamiltonian and show no evidence for spectral congestion due to intramolecular vibrational coupling, which bodes well for high resolution studies of other ring radicals and polycyclic aromatic hydrocarbons. In summary, the combination of slit jet discharge methods with high resolution infrared lasers enables spectroscopic investigation of even highly reactive combustion and interstellar radical intermediates under gas phase, jet-cooled (T rot ≈ 11 K) conditions.

Description: The paper deals with a model-free approach to the analysis of quasielastic neutron scattering intensities from anomalously diffusing quantum particles. All quantities are inferred from the asymptotic form of their time-dependent mean square displacements which grow ∝ t α , with 0 ≤ α 〈 2. Confined diffusion ( α = 0) is here explicitly included. We discuss in particular the intermediate scattering function for long times and the Fourier spectrum of the velocity autocorrelation function for small frequencies. Quantum effects enter in both cases through the general symmetry properties of quantum time correlation functions. It is shown that the fractional diffusion constant can be expressed by a Green-Kubo type relation involving the real part of the velocity autocorrelation function. The theory is exact in the diffusive regime and at moderate momentum transfers.

Description: Adiabatic approximations in time-dependent density functional theory (TDDFT) will in general yield unphysical time-dependent shifts in the resonance positions of a system driven far from its ground-state. This spurious time-dependence is explained in Fuks et al. [Phys. Rev. Lett. 114 , 183002 (2015)] in terms of the violation of an exact condition by the non-equilibrium exchange-correlation kernel of TDDFT. Here we give details on the derivation and discuss reformulations of the exact condition that apply in special cases. In its most general form, the condition states that when a system is left in an arbitrary state, the TDDFT resonance position for a given transition in the absence of time-dependent external fields and ionic motion is independent of the state. Special cases include the invariance of TDDFT resonances computed with respect to any reference interacting stationary state of a fixed potential, and with respect to any choice of appropriate stationary Kohn-Sham reference state. We then present several case studies, including one that utilizes the adiabatically exact approximation, that illustrate the conditions and the impact of their violation on the accuracy of the ensuing dynamics. In particular, charge-transfer across a long-range molecule is hampered, and we show how adjusting the frequency of a driving field to match the time-dependent shift in the charge-transfer resonance frequency results in a larger charge transfer over time.

Description: We perform molecular dynamics simulations to investigate the static and dynamic fragmentation of metallic liquid sheets of tin induced by random surface fluctuations. The static regime is analyzed by simulating sheets of different thicknesses, and the dynamic fragmentation is ensured by applying along the longitudinal direction of a sheet an instantaneous expansion velocity per initial unit length (expansion rate) with values ranging from 1 × 10 9 to 3 × 10 10  s −1 . The simulations show that the static/dynamic fragmentation becomes possible when the fluctuations of the upper and lower surfaces of the sheets can either overlap or make the local volume density of the system go down below a critical value. These two mechanisms cause locally in the sheet the random nucleation of pores of void, on a timescale that exponentially increases with the sheet thickness. Afterwards, the pores develop following distinct stages of growth, coalescence, and percolation, and later in time aggregates of liquid metal are formed. The simulations also show that the fragmentation of static sheets is characterized by relatively mono-dispersed surface and volume distributions of the pores and aggregates, respectively, whereas in extreme conditions of dynamic fragmentation (expansion rate typically in the range of 1 × 10 10  s −1 ), the distributions are rather poly-dispersed and obey a power law decay with surface (volume). A model derived from the simulations suggests that both dynamic and static regimes of fragmentation are similar for expansion rates below typically 1 × 10 7  s −1 .

Description: Multicomponent density functional theory (DFT) methods have been developed to treat two types of particles, such as electrons and nuclei, quantum mechanically at the same level. In the nuclear-electronic orbital (NEO) approach, all electrons and select nuclei, typically key protons, are treated quantum mechanically. For multicomponent DFT methods developed within the NEO framework, electron-proton correlation functionals based on explicitly correlated wavefunctions have been designed and used in conjunction with well-established electronic exchange-correlation functionals. Herein a general theory for multicomponent embedded DFT is developed to enable the accurate treatment of larger systems. In the general theory, the total electronic density is separated into two subsystem densities, denoted as regular and special, and different electron-proton correlation functionals are used for these two electronic densities. In the specific implementation, the special electron density is defined in terms of spatially localized Kohn-Sham electronic orbitals, and electron-proton correlation is included only for the special electron density. The electron-proton correlation functional depends on only the special electron density and the proton density, whereas the electronic exchange-correlation functional depends on the total electronic density. This scheme includes the essential electron-proton correlation, which is a relatively local effect, as well as the electronic exchange-correlation for the entire system. This multicomponent DFT-in-DFT embedding theory is applied to the HCN and FHF − molecules in conjunction with two different electron-proton correlation functionals and three different electronic exchange-correlation functionals. The results illustrate that this approach provides qualitatively accurate nuclear densities in a computationally tractable manner. The general theory is also easily extended to other types of partitioning schemes for multicomponent systems.

Description: We report on the computational design of an all-metal aromatic sandwich, [Sb 4 Au 4 Sb 4 ] 2− . The triple-layered, square-prismatic sandwich complex is the global minimum of the system from Coalescence Kick and Minima Hopping structural searches. Following a standard, qualitative chemical bonding analysis via canonical molecular orbitals, the sandwich complex can be formally described as [Sb 4 ] + [Au 4 ] 4− [Sb 4 ] + , showing ionic bonding characters with electron transfers in between the Sb 4 /Au 4 /Sb 4 layers. For an in-depth understanding of the system, one needs to go beyond the above picture. Significant Sb → Au donation and Sb ← Au back-donation occur, redistributing electrons from the Sb 4 /Au 4 /Sb 4 layers to the interlayer Sb–Au–Sb edges, which effectively lead to four Sb–Au–Sb three-center two-electron bonds. The complex is a system with 30 valence electrons, excluding the Sb 5s and Au 5d lone-pairs. The two [Sb 4 ] + ligands constitute an unusual three-fold (π and σ) aromatic system with all 22 electrons being delocalized. An energy gap of ∼1.6 eV is predicted for this all-metal sandwich. The complex is a rare example for rational design of cluster compounds and invites forth-coming synthetic efforts.

Description: We employ a field-theoretical variational approach to study the behavior of ionic solutions in the grand canonical ensemble. To describe properly the hardcore interactions between ions, we use a cutoff in Fourier space for the electrostatic contribution of the grand potential and the Carnahan-Starling equation of state with a modified chemical potential for the pressure one. We first calibrate our method by comparing its predictions at room temperature with Monte Carlo results for excess chemical potential and energy. We then validate our approach in the bulk phase by describing the classical “ionic liquid-vapor” phase transition induced by ionic correlations at low temperature, before applying it to electrolytes at room temperature confined to nanopores embedded in a low dielectric medium and coupled to an external reservoir of ions. The ionic concentration in the nanopore is then correctly described from very low bulk concentrations, where dielectric exclusion shifts the transition up to room temperature for sufficiently tight nanopores, to high concentrations where hardcore interactions dominate which, as expected, modify only slightly this ionic “capillary evaporation.”

Description: The Orsay-Trento bosonic density functional theory model is extended to include dissipation due to the viscous response of superfluid 4 He present at finite temperatures. The viscous functional is derived from the Navier-Stokes equation by using the Madelung transformation and includes the contribution of interfacial viscous response present at the gas-liquid boundaries. This contribution was obtained by calibrating the model against the experimentally determined electron mobilities from 1.2 K to 2.1 K along the saturated vapor pressure line, where the viscous response is dominated by thermal rotons. The temperature dependence of ion mobility was calculated for several different solvation cavity sizes and the data are rationalized in the context of roton scattering and Stokes limited mobility models. Results are compared to the experimentally observed “exotic ion” data, which provides estimates for the corresponding bubble sizes in the liquid. Possible sources of such ions are briefly discussed.

Description: Sixty-four neutral density filters constructed of metal plates with 88 apertures of varying diameter have been radiographed with a soft x-ray source and CCD camera at National Security Technologies, Livermore. An analysis of the radiographs fits the radial dependence of the apertures’ image intensities to sigmoid functions, which can describe the rapidly decreasing intensity towards the apertures’ edges. The fitted image intensities determine the relative attenuation value of each filter. Absolute attenuation values of several imaged filters, measured in situ during calibration experiments, normalize the relative quantities which are now used in analyses of neutron spectrometer data at the National Ignition Facility.

Description: The objective of this paper is to demonstrate that the addition of properly tuned nonlinearities to a nonlinear system can increase the range over which a specific resonance responds linearly. Specifically, we seek to enforce two important properties of linear systems, namely, the force-displacement proportionality and the invariance of resonance frequencies. Numerical simulations and experiments are used to validate the theoretical findings.

Description: HoCrO 3 , Ho 0.67 Gd 0.33 CrO 3 , and GdCrO 3 bulk powder samples were prepared by citrate route. The phase purity and the structural properties of the samples were examined by x-ray diffraction and Raman spectroscopic measurements. The dc magnetization data revealed that the Cr 3+ ordering temperatures (Néel temperature) for the HoCrO 3 , Ho 0.67 Gd 0.33 CrO 3 , and GdCrO 3 samples are 140 K, 148 K, and 167 K, respectively, while the ac magnetization data revealed that the rare-earth (Ho) ordering occurs at ∼8 K for HoCrO 3 and Ho 0.67 Gd 0.33 CrO 3 samples. Temperature-induced magnetization reversal and spin reorientation were observed in GdCrO 3 bulk sample, which depends on applied magnetic field and disappears at ∼1500 Oe and 500 Oe, respectively. By fitting the dc magnetic data with Curie-Weiss law, the effective magnetic moments were calculated to be 11.66 μ B , 10.23 μ B , and 9.90 μ B for the HoCrO 3 , Ho 0.67 Gd 0.33 CrO 3 , and GdCrO 3 samples, respectively. The isothermal magnetization data showed that the magnetic behavior changed from canted antiferromagnetic in low temperature region (below Néel temperature) to paramagnetic at high temperature. It was found that Gd substitution considerably improves the magnetocaloric effect of HoCrO 3 . Pure GdCrO 3 bulk sample showed giant magnetocaloric entropy change (31.6 J/kg K at temperature ∼5 K and at ∼70 kOe), which is higher than that for polycrystalline RMnO 3 , RCrO 3 , and RFeO 3 bulk powder samples. This renders GdCrO 3 useful for potential applications in low-temperature magnetic refrigeration.

Description: Electric field-induced changes in the domain wall motion of (1−x)Bi(Mg 0.5 Ti 0.5 )O 3 –xPbTiO 3 (BMT-xPT) near the morphotropic phase boundary (MPB) where x = 0.37 (BMT-37PT) and x = 0.38 (BMT-38PT), are studied by means of synchrotron x-ray diffraction. Through Rietveld analysis and profile fitting, a mixture of coexisting monoclinic ( Cm ) and tetragonal ( P 4 mm ) phases is identified at room temperature. Extrinsic contributions to the property coefficients are evident from electric-field-induced domain wall motion in both the tetragonal and monoclinic phases, as well as through the interphase boundary motion between the two phases. Domain wall motion in the tetragonal and monoclinic phases for BMT-37PT is larger than that of BMT-38PT, possibly due to this composition's closer proximity to the MPB. Increased interphase boundary motion was also observed in BMT-37PT. Lattice strain, which is a function of both intrinsic piezoelectric strain and elastic interactions of the grains (the latter originating from domain wall and interphase boundary motion), is similar for the respective tetragonal and monoclinic phases.

Description: We fabricated homogeneous double-layer amorphous Si-doped indium oxide (ISO) thin-film transistors (TFTs) with an insulating ISO cap layer on top of a semiconducting ISO bottom channel layer. The homogeneously stacked ISO TFT exhibited high mobility (19.6 cm 2 /V s) and normally-off characteristics after annealing in air. It exhibited normally-off characteristics because the ISO insulator suppressed oxygen desorption, which suppressed the formation of oxygen vacancies (V O ) in the semiconducting ISO. Furthermore, we investigated the recovery of the double-layer ISO TFT, after a large negative shift in turn-on voltage caused by hydrogen annealing, by treating it with annealing in ozone. The recovery in turn-on voltage indicates that the dense V O in the semiconducting ISO can be partially filled through the insulator ISO. Controlling molecule penetration in the homogeneous double layer is useful for adjusting the properties of TFTs in advanced oxide electronics.

Description: A compact and integrated optical gas sensor on a silicon-on-insulator platform based on surface plasmon interference for hydrogen detection is theoretically introduced in this paper. The basic sensor element consists of a thin layer of palladium (Pd) embedded in a silicon waveguide. Two decoupled surface plasmon polariton waves propagate simultaneously on either side of the Pd layer, which combine and interfere at the end of the Pd layer. The interference mode can be either constructive or destructive, which is highly sensitive to volumetric hydrogen concentration. The proposed sensor is of great potential as a basic building block for lab-on-chip-scale devices owing to its high integration and compactness.

Description: A study is performed on a photonic-state mixing-pattern in an insulator-metal-insulator cylindrical silver nanoshell and its rich variations induced by changes in the geometry and dielectric media of the system, representing the combined influences of plasmon coupling strength and cavity effects. This study is performed in terms of the photonic local density of states (LDOS) calculated using the Green tensor method, in order to elucidate those combined effects. The energy profiles of LDOS inside the dielectric core are shown to exhibit consistently growing number of redshifted photonic states due to an enhanced plasmon coupling induced state mixing arising from decreased shell thickness, increased cavity size effect, and larger symmetry breaking effect induced by increased permittivity difference between the core and the background media. Further, an increase in cavity size leads to increased additional peaks that spread out toward the lower energy regime. A systematic analysis of those variations for a silver nanoshell with a fixed inner radius in vacuum background reveals a certain pattern of those growing number of redshifted states with an analytic expression for the corresponding energy downshifts, signifying a photonic state mixing scheme beyond the commonly adopted plasmon hybridization scheme. Finally, a remarkable correlation is demonstrated between the LDOS energy profiles outside the shell and the corresponding scattering efficiencies.

Description: In this paper, we present a new canonical replica exchange molecular dynamics (REMD) simulation method with normal pressure for all replicas (REMD- NV ( p ) T ). This method is suitable for systems for which conventional constant NPT -setups are difficult to implement. In this implementation, each replica has an individual volume, with normal pressure maintained for each replica in the simulation. We derive a novel exchange term and validate this method on the structural properties of SPC/E water and dialanine ( Ala 2 ) in the bulk and in the presence of a graphene layer. Compared to conventional constant NPT -REMD and NVT -REMD simulations, we find that the structural properties of our new method are in good agreement with simulations in the NPT -ensemble at all temperatures. The structural properties of the systems considered are affected by high pressures at elevated temperatures in the constant NVT -ensemble, an effect that our method corrects for. Unprojected distributions reveal that essential motions of the peptide are affected by the presence of the barostat in the NPT implementation but that the dynamical eigenmodes of the NV(p)T method are in close quantitative agreement with the NVT-ensemble.

Description: In order to study the dependence of water solubility and hydration behavior of nanoparticles on their surface polarity, we designed polar nanoparticles with varying surface polarity by assigning atomic partial charge to the surface of C60. The water solubility of the nanoparticle is enhanced by several orders of magnitude after the introduction of surface polarity. Nevertheless, when the atomic partial charge grows beyond a certain value ( q M ), the solubility continuously decreases to the level of nonpolar nanoparticle. It should be noted that such q M is comparable with atomic partial charge of a variety of functional groups. The hydration behaviors of nanoparticles were then studied to investigate the non-monotonic dependence of solubility on the surface polarity. The interaction between the polar nanoparticle and the hydration water is stronger than the nonpolar counterpart, which should facilitate the dissolution of the nanoparticles. On the other hand, the surface polarity also reduces the interaction of hydration water with the other water molecules and enhances the interaction between the nanoparticles which may hinder their dispersion. Besides, the introduction of surface polarity disturbs and even rearranges the hydration structure of nonpolar nanoparticle. Interestingly, the polar nanoparticle with less ordered hydration structure tends to have higher water solubility.

Description: We study the translational single particle dynamics of hydration water of lysozyme upon cooling by means of molecular dynamics simulations. We find that water close to the protein exhibits two distinct relaxations. By characterizing their behavior upon cooling, we are able to assign the first relaxation to the structural α -relaxation also present in bulk water and in other glass-forming liquids. The second, slower, relaxation can be ascribed to a dynamic coupling of hydration water motions to the fluctuations of the protein structure. Both relaxation times exhibit crossovers in the behavior upon cooling. For the α -process, we find upon cooling a crossover from a fragile behavior to a strong behavior at a temperature which is about five degrees higher than that of bulk water. The long -relaxation time appears strictly connected to the protein motion as it shows upon cooling a temperature crossover from a strong behavior with a lower activation energy to a strong behavior with a higher activation energy. The crossover temperature coincides with the temperature of the protein dynamical transition. These findings can help experimentalists to disentangle the different information coming from total correlators and to better characterize hydration water relaxations in different biomolecules.

Description: We extend a previously introduced model of stochastic gene regulation of cancer to a nonlinear case having both gene and pseudogene messenger RNAs (mRNAs) self-regulated. The model consists of stochastic Boolean genetic elements and possesses noise-induced multistability (multimodality). We obtain analytical expressions for probabilities for the case of constant but finite number of microRNA molecules which act as a noise source for the competing gene and pseudogene mRNAs. The probability distribution functions display both the global bistability regime as well as even-odd number oscillations for a certain range of model parameters. Statistical characteristics of the mRNA’s level fluctuations are evaluated. The obtained results of the extended model advance our understanding of the process of stochastic gene and pseudogene expressions that is crucial in regulation of cancer.

Description: We analyse van der Waals interactions between a pair of dielectrically anisotropic plane-layered media interacting across a dielectrically isotropic solvent medium. We develop a general formalism based on transfer matrices to investigate the van der Waals torque and force in the limit of weak birefringence and dielectric matching between the ordinary axes of the anisotropic layers and the solvent. We apply this formalism to study the following systems: (i) a pair of single anisotropic layers, (ii) a single anisotropic layer interacting with a multilayered slab consisting of alternating anisotropic and isotropic layers, and (iii) a pair of multilayered slabs each consisting of alternating anisotropic and isotropic layers, looking at the cases where the optic axes lie parallel and/or perpendicular to the plane of the layers. For the first case, the optic axes of the oppositely facing anisotropic layers of the two interacting slabs generally possess an angular mismatch, and within each multilayered slab the optic axes may either be the same or undergo constant angular increments across the anisotropic layers. In particular, we examine how the behaviors of the van der Waals torque and force can be “tuned” by adjusting the layer thicknesses, the relative angular increment within each slab, and the angular mismatch between the slabs.

Description: The static and dynamic first ( β ‖ ) and second ( γ ‖ ) hyperpolarizabilities of water, methanol, and dimethyl ether have been evaluated within the response function approach using a hierarchy of coupled cluster levels of approximation and doubly augmented correlation consistent atomic basis sets. For the three compounds, the electronic β ‖ and γ ‖ values calculated at the CCSD and CC3 levels are in good agreement with gas phase electric field-induced second harmonic generation (EFISHG) measurements. In addition, for dimethyl ether, the frequency dispersion of both properties follows closely recent experimental values [V. W. Couling and D. P. Shelton, J. Chem. Phys. 143 , 224307 (2015)] demonstrating the reliability of these methods and levels of approximation. This also suggests that the vibrational contributions to the EFISHG responses of these molecules are small.

Description: Resonance-enhanced multiphoton ionization (REMPI) is a widely used technique for studying molecular photoionization and producing molecular cations for spectroscopy and dynamics studies. Here, we present a model for describing hyperfine-structure effects in the REMPI process and for predicting hyperfine populations in molecular ions produced by this method. This model is a generalization of our model for fine- and hyperfine-structure effects in one-photon ionization of molecules presented in Paper I [M. Germann and S. Willitsch, J. Chem. Phys. 145 , 044314 (2016)]. This generalization is achieved by covering two main aspects: (1) treatment of the neutral bound-bound transition including the hyperfine structure that makes up the first step of the REMPI process and (2) modification of our ionization model to account for anisotropic populations resulting from this first excitation step. Our findings may be used for analyzing results from experiments with molecular ions produced by REMPI and may serve as a theoretical background for hyperfine-selective ionization experiments.

Description: A design to extend the unique divertor Thomson scattering system on DIII-D to allow measurements of electron temperature and density in high triangularity plasmas is presented. Access to this region is selectable on a shot-by-shot basis by redirecting the laser beam of the existing divertor Thomson system inboard — beneath the lower floor using a moveable, high-damage threshold, in-vacuum mirror — and then redirecting again vertically. The currently measured divertor region remains available with this mirror retracted. Scattered light is collected from viewchords near the divertor floor using in-vacuum, high temperature optical elements and relayed through the port window, before being coupled into optical fiber bundles. At higher elevations from the floor, measurements are made by dynamically re-focusing the existing divertor system collection optics. Nd:YAG laser timing, analysis of the scattered light spectrum via polychromators, data acquisition, and calibration are all handled by existing systems or methods of the current multi-pulse Thomson scattering system. Existing filtered polychromators with 7 spectral channels are employed to provide maximum measurement breadth ( T e in the range of 0.5 eV–2 keV, n e in the range of 5 × 10 18 –1 × 10 21 m 3 ) for both low T e in detachment and high T e measurement up beyond the separatrix.

Description: The Landau-Ginzburg-Wilson paradigm is proposed as a framework, to investigate the conformational landscape of intrinsically unstructured proteins. A universal C α -trace Landau free energy is deduced from general symmetry considerations, with the ensuing all-atom structure modeled using publicly available reconstruction programs Pulchra and Scwrl . As an example, the conformational stability of an amyloid precursor protein intra-cellular domain (AICD) is inspected; the reference conformation is the crystallographic structure with code 3DXC in Protein Data Bank (PDB) that describes a heterodimer of AICD and a nuclear multi-domain adaptor protein Fe65. Those conformations of AICD that correspond to local or near-local minima of the Landau free energy are identified. For this, the response of the original 3DXC conformation to variations in the ambient temperature is investigated, using the Glauber algorithm. The conclusion is that in isolation the AICD conformation in 3DXC must be unstable. A family of degenerate conformations that minimise the Landau free energy is identified, and it is proposed that the native state of an isolated AICD is a superposition of these conformations. The results are fully in line with the presumed intrinsically unstructured character of isolated AICD and should provide a basis for a systematic analysis of AICD structure in future NMR experiments.