Low Wavenumber Region Research Articles

Structural, Morphological, Optical and Vibrational Properties of a Novel Coral-Like Fibrous CuO Nanostructure Synthesized via Dropwise Precipitation for UV-light Induced Photocatalytic Wastewater Remediation on Aqueous R6G Dye

CuO is a well-known monoclinic structure with unique properties that is extensively investigated for sensor, energy storage, and optoelectronic applications. In this work, the CuO nanostructure was synthesized through facile precipitation by mixing the aqueous copper (II) sulfate pentahydrate with sodium hydroxide. The as-synthesized CuO was characterized by scanning electron microscopy (SEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR) and UV–visible spectroscopy. A homogeneous growth of a narrow, fine coral-like fibrous morphology was observed on CuO under SEM imaging. The FTIR spectra reveal the existence of some dominant sharp bands in the lower wavenumber region that represent the Cu-O bonds. The high solubility of CuO in water confirms the formation of particles with nanoscale dimensions. CuO exhibits a strong optical absorption peak at 510 nm, and the band gap determined by Tauc's relation is 2.11 eV. CuO is capable of inducing photocatalytic degradation on R6G dye solutions under low-intensity UVC irradiation, which can serve as a future photocatalyst for wastewater treatment.

SERS activity of silver nanoparticles and silver-modified 2D graphitic carbon nitride towards ciprofloxacin drug

Herein, silver nanoparticles (AgNPs) and silver-loaded graphitic carbon nitride (Ag@g-C3N4) nanocomposites have been synthesized and used as an effective surface-enhanced Raman scattering (SERS) substrates for the detection of low concentrations (10-14 M) of ciprofloxacin (CIP), a commonly bioactive medication used to treat bacterial illnesses. A combined approach of vibrational spectroscopy and density functional theory (DFT) has been developed to understand the possible modes of analyte (CIP) and SERS substrate (AgNPs and Ag@g-C3N4) interactions. Furthermore, it has been noticed that the behavior of drug molecules in terms of SERS response and energetics of interaction changed significantly when interacted with the noble metal AgNPs decorated onto the g-C3N4 framework in comparison to only AgNPs as substrate. The most prominent interaction scenario between AgNPs and CIP is likely to be through the –NH moiety of drug molecule with an interaction energy of −306 kcal/mol. Whereas, the CIP molecules adsorbed onto Ag@g-C3N4 nanocomposite were more flexible with interaction energy of −107 kcal/mol, suggesting a greater association of analyte with the skeletal modes of substrate leading to Raman enhancements in the low wavenumber region i.e. below 600 cm−1. Hence, the Ag@g-C3N4 nanocomposite-based SERS substrates investigated served two distinct spectral ranges, making them complementary of each other in terms of SERS detection of CIP. The characteristics of the computed frontier molecular orbitals indicated a pronounced amount of charge transfer between the drug and the substrate, highlighting the significance of the chemical mechanism of the overall process. These results represent a successful approach to have an extended spectral range that covers lower wavenumber shifts by applying simple and meaningful modifications to the normally utilized noble metal-based nanoparticles, which can lead to more effective and reliable detection of bioactive drugs.

Pressure-induced phase changes in natural fluorapophyllite-(K) studied by Raman spectroscopy

The high-pressure Raman spectra in the low-wavenumber region (50–1200 cm−1) and the hydroxyl stretching vibration region (2600–3800 cm−1) of fluorapophyllite-(K) were collected in the interval of 0.0–50.7 GPa. Experimental results show that fluorapophyllite-(K) undergoes a crystalline-crystalline phase transition from a tetragonal structure (P4/mnc) to an orthorhombic structure (Pnnm) and then amorphization under high pressure conditions. Discontinuous changes in Raman peaks in the hydroxyl vibration region (2600–3800 cm−1) and the low-wavenumber region (50–1200 cm−1) occur at different onset pressures, suggesting that the destabilization of sub-lattices in fluorapophyllite-(K) under high pressure is not synchronous; the weak interlayer H2O structural units are more prone to destabilization at lower pressures than the rigid SiO4 tetrahedral layer units. Therefore, H2O groups in fluorapophyllite-(K) serve as sensitive local probes during the pressure-induced phase transition and amorphization.

A novel high hardness and low loss Mg5Ga2Sn2O12 ceramic with spinel-structure

Inorganic oxides with a spinel structure play an indispensable role in various applications because of their stability and exceptional performance. This study prepared Mg5Ga2Sn2O12 ceramics using the solid-state method. TEM analysis reveals that the ceramics show local lattice distortions. When the sintering temperature is 1480 °C, the relative density and Vickers hardness of Mg5Ga2Sn2O12 ceramics are 96.8 % and 12.58 GPa, respectively. The Mg5Ga2Sn2O12 ceramics exhibit optimum microwave dielectric properties, with εr = 8.57, Q × f = 138,769 GHz, and τf = −24.7 ppm/°C. Far-infrared fitting shows that the vibration mode in the low-wave number region has a significant influence on the dielectric properties of ceramics. The P–V−L theory indicates that the Sn–O bond has the most significant influence on εr and Q × f. Given these advantages, Mg5Ga2Sn2O12 ceramics hold promise for applications in low-loss dielectric materials.

Gravitational effects on large-scale premixed flame dynamics: From linear to nonlinear evolution

Gravitational effects on premixed flame propagation, coupled with Darrieus–Landau instability, are investigated through direct numerical simulations under both thermal-diffusive (TD) stable and unstable situations. During the early stage of propagation, the dispersion relation between the linear growth rate σ and wavenumber k of perturbations exhibits good symmetry, allowing it to be well-fitted by the polynomial σ=c+ak−bk2. The modified Clavin–Garcia relation derived from asymptotic analysis aligns with numerical results only in the low-wavenumber region, since the significant error in the second-order coefficient bg renders it inapplicable for the high-wavenumber region. In the nonlinear regime, three morphological effects of gravity on the flame propagation have been identified: flattening the flame front, suppressing the cusp fusion rate, and promoting the new cusp generation (front splitting). The first two effects slow down the flame propagation, respectively, by reducing the overall flame front length and delaying the appearance of velocity peaks. Nevertheless, the promotion of front splitting accelerates the flame by facilitating more frequent velocity peaks arising from both cusp generation and fusion events. These various morphological effects, along with their distinct impacts on either accelerating or decelerating the flame propagation, result in significant variations in the behavior of large-scale flame propagation under different gravitational levels, despite gravity being a large-scale stabilizing effect.

Thermal annealing gradient tailoring on ammonium nitrate-capped CdS nanospheres synthesized via green precipitation

This study explores the impact of thermal annealing gradients on the physical properties and structural evolution of cadmium sulphide (CdS) nanospheres capped with ammonium nitrate as a modifier, which were fabricated through precipitation and subsequent annealing within 160–480 °C temperature range. The properties were characterized using X-ray diffraction (XRD), ultraviolet–visible (UV–Vis), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques The XRD results show that the present CdS exhibits superior crystallinity compared to pure CdS without capping, transitions from a cubic to a hexagonal phase structure, and increases in crystallite size and crystallinity with increasing temperature. The FTIR spectra postulate that a vibrational band presence evidences ammonium nitrate capping on CdS, with another distinct band that represents CdS in the lower wavenumber region, both intensifying at elevated temperatures. The UV–Vis analysis reveals that CdS exhibits strong ultraviolet (UV) absorption suitable for effective photoreaction under UV light and has a broader band gap compared to bulk CdS. SEM images show an extensive distribution of homogeneous nanospheres over the surface, with increased growth in size when capped with ammonium nitrate and at higher temperatures. As validated by TGA and DSC results, CdS with a smaller crystallite size improves thermal stability and energy transfer, as evidenced by reduced weight loss and a lower endothermic temperature, respectively. Varying the annealing temperature with ammonium nitrate capping can improve the structural and physical properties of CdS, which are beneficial for varied applications such as optoelectronics, energy storage, and photocatalysts.

Experimental-computational study on the competition between 1,2-dimethoxyethane and tetrahydrofuran in a MACC-based electrolyte

The 1:1 MgCl2:AlCl3 (MACC)-based electrolyte was spectroscopically investigated for the first time in the presence of an equimolal 1,2-dimethoxyethane (DME):tetrahydrofuran (THF) mixture. Composition-dependent Raman spectra suggested that the new bands at 896 and 883 cm−1 correspond to the mixed νCO and νCC vibrations of both ethers coordinated to Mg(II) ions. A signal at 219 cm−1, which is assigned to the νMgCl vibration, was only observed for the highest acid-base pair content, in contrast to the behavior exhibited in the acyclic ether alone. Density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations revealed that the [MgCl(DME)(THF)3]+ and [MgCl(DME)2THF]+ monomers may be associated to the experimental bands observed at the solvent region, thus being predicted at 867 and 858 cm−1, respectively. The [Mg2(μ-Cl)2(DME)4]2+ dimer has a theoretical band at 216 cm−1, which is related to the experimentally observed signal at the low wavenumber region. The preferential solvation effect is discussed in detail for the studied solvates.

On the challenges of estimating the low-wavenumber wall pressure field beneath a turbulent boundary layer using a microphone array

The low-wavenumber components of the turbulent boundary layer (TBL) wall pressure field (WPF) are known to be the primary cause of structural vibration in low-Mach number flows, despite the maximal energy of the TBL being at the convective wavenumber. Existing semi-empirical TBL models show good agreement in predicting the WPF levels in convective region but differ significantly in the low-wavenumber domain. This study aims to highlight the challenges of estimating the low-wavenumber WPF in a TBL using a microphone array. A regularized Fourier-based approach is proposed to numerically study the estimation of the low-wavenumber WPF. Performance of the proposed method is initially evaluated by comparing the estimated WPF against a closed-form input TBL model. Effects of sensor spacing, co-array factor, and sensor distribution on the estimation of the low-wavenumber WPF levels are then investigated. To mimic experimental measurements a virtual acoustic experiment is proposed, involving the synthesis of snapshots of TBL-induced WPF. It is demonstrated that although with relatively small number of snapshots the convective region can be identified, a significant number of snapshots is required to well estimate the TBL low-wavenumber region.

Green synthesis of emerging ZnO and Ca-doped ZnO nanoparticles towards optical, magnetic properties and its antibacterial application

A green synthesis method is adopted to prepare emerging low cost ZnO (ZNP) and Ca substitute ZnO nanoparticles (CZNP) using Psidium guajava fruit (PGF) extract as an effective reducing and capping agent. An X-ray diffraction study of the synthesized nanoparticles revealed that they have a hexagonal wurtzite structure. The elemental compositions and oxidation states of ZNP and CZNP surfaces are quantified. The HRSEM image shows the nano-flake like structure of the synthesized nanomaterials ZNP and CZNP samples. The elemental compositions were identified using EDAX spectra. From the Raman spectra, the low wavenumber region of 2nd order Raman modes at 341 and 346 cm-1 were ascribed to the difference E2 high-E2 low. Kubelka–Munk (K–M) method is used for estimating direct band gap and it is 3.3 eV and 3.04 eV for ZNP and CZNP respectively. Due to the zinc and oxygen vacancies, six different bands were observed in the photoluminescence spectra. The TG analysis was observed 5.6% of weight loss for ZNP and 5.8% of weight loss for CZNP sample. The Magnetization–Field (M–H) hysteresis curves revealed the appearance of diamagnetic behavior at room temperature. The asfabricated pure ZnO and Ca-doped ZnO nanoparticles were evaluated for the antibacterial activity. The Ca substituted ZnO sample showed higher antibacterial activity than pure ZnO sample.

Significant phonon assignments in multiferroic BiFeO3 single crystal

In the present work, the technique of Back Scattering Micro-Raman was employed at low and room temperatures in order to examine all the possible phonon vibration modes present in a crystal of BiFeO3(BFO). The observation & identification of all E (TO), E (LO), A1 (TO), and A1 (LO) normal modes was sucessfully accomplished. The low temperature Raman spectroscopy measurements showed two one-magnon branches, σ-magnon at 20.06 cm−1 and γ-magnon at 26.93 cm−1. The spectral characteristics of the three A1 (LO) modes were observed at roughly 176.63 cm−1, 225.93 cm−1 and 505.53 cm−1, exhibiting low intensity longitudinal optical modes. The observed peaks at 145.34 cm−1, 223.92 cm−1, 292.54 cm−1, and 552.18 cm−1 were identified and categorized as A1 (TO) modes. E (TO) peaks were observed at 73.30 cm-1, 131.94 cm-1, 239.35 cm-1, 265.04 cm-1, 278.45 cm-1, 349.95 cm-1, 374.69 cm-1, 441.04 cm-1, 522.99 cm-1. In addition, E(LO) peaks were observed at 80.76 cm-1, 175.03 cm-1, 241.59 cm-1, 275.42 cm-1, 346.92 cm-1, 371.34 cm-1, 419.38 cm-1, and 469.65 cm-1.

Simultaneous bond-selective deuterium-based isotopic labeling sensing with disposable ultra-miniature CARS fiber probe.

Deuterium-based isotopic labeling is an important technique for tracking cellular metabolism with the Raman signals analysis of low-wavenumber (LW) C-D bonds and high-wavenumber (HW) C-H bonds. We propose and demonstrate a disposable ultra-miniature fiber probe to detect LW and HW coherent anti-Stokes Raman scattering (CARS) spectra for deuterated compounds simultaneously and bond-selectively sensing. The 10.78 µm diameter disposable fiber probe, comprised of focusing taper as fiber probe head and time-domain walk-off eliminating fiber section with designed length, realizes wide-frequency-interval dual Stokes pulse delivering and focusing. The fiber probe enables quantitative concentration determination with resolution down to 11 mM. The chemical vibration modes of LW region C-D bonds and HW region C-H bonds of the mixture samples of organic compounds and their deuterated counterparts in a simulated cell are simultaneously excited and characterized. The CARS disposable fiber probe introduces a promising handle for in vivo biochemical detection based on isotopic labeling sensing.

Attenuated Total Reflection Fourier Transform Infrared Spectroscopy with Soft Independent Modeling of Class Analogy-Principal Component Analysis for Classifying Cotton Fiber Maturity Phenotypes of Cotton Population Composed of Various Genotypes.

Maturity is a major fiber trait that affects the processing and performance of cotton fiber. Rapid and accurate identification of fiber maturity phenotypes and genotypes is of importance to breeders. Previous studies showed that either conventional fiber measurements or attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) analysis discriminated the immature fiber (im) phenotype from the wild type (WT) mature fiber phenotype in a segregating F2 population from a cross between two upland cotton lines differing in fiber maturity. However, both conventional fiber property measurement methods and FT-IR analyses with current algorithms could not detect the subtle differences among the WT fibers composed of two different genotypes, WT homozygosity (WT-homo) and WT heterozygosity (WT-hetero). This research explored the FT-IR method, in combination with soft independent modeling of class analogy of principal component analysis (SIMCA-PCA), for the discrimination of WT fiber phenotypes consisting of two different genotypes (WT-homo and WT-hetero). The new approach enabled the detection of IR spectral intensity differences between WT-homo and WT-hetero fibers. Successful classification originated from a distinctive spectral difference in the low-wavenumber region (<700 cm-1) between WT-hetero fibers and WT-homo fibers. This observation emphasized that ATR FT-IR with a SIMCA-PCA approach would be a sensitive tool for classifying the WT fibers demonstrating minor phenotypic differences. The improved sensitivity of the infrared method may provide a way of dissecting genotype-phenotype interactions of cotton fibers rapidly and efficiently.

Spectroscopic features of dissolved iodine in pristine and gamma-irradiated nitric acid solutions

While iodine speciation is important for a wide range of nuclear safety activities, understanding the mechanisms of the transformations of iodine between chemical forms and the sensitivity of these transitions to solution conditions and exposure to radiation remains an active area of research. This work curates spectroscopic data from several experimental techniques and establishes their sensitivity and limitations in detecting changes in iodine speciation in both neutral and acidic regimes. The techniques include Raman spectroscopy, Fourier Transform Infrared (FTIR) spectroscopy, 127I nuclear magnetic resonance (NMR) spectroscopy, and ultraviolet–visible (UV–Vis) spectroscopy. Analysis of these data indicates that these commonly accessible spectroscopies often have dynamic ranges of measurable concentrations that do not always overlap between all techniques. The experimental techniques are disparately sensitive to iodide (I−), molecular iodine (I2), triiodide (I3−) iodate (IO3−), and periodate (IO4−) species. Raman, FTIR, and NMR spectra were subsequentially analyzed using two-dimensional correlation analyses to generate high-resolution autocorrelation spectra. The use of these spectroscopies is then extended to tracking acidification-induced and gamma irradiation-induced transformations of dissolved sodium iodide in deionized water and concentrated nitric acid. Both dissolution into nitric acid and irradiation with a gamma source are demonstrated to perturb the iodine speciation promoting their assembly into I2 and/or I3−. While I2 and I3− species are undetectable with FTIR spectroscopy and 127I NMR spectroscopy, the species can be detected with UV–Vis spectroscopy, and in some instances, I3− can be detected with Raman spectroscopy in the low wavenumber region. Ultimately, the results of this work provide a path to designing optimal combinations of techniques to detect forms of iodine across a wide range of concentrations and conditions.

Reducing the low-wavenumber dispersion error by building the Lagrange dual problem with a powerful local restriction

Abstract The broadband finite-difference (FD) coefficients computed by a cost function have been widely applied to suppress of numerical dispersion. Under the same conditions, the FD coefficients with small low-wavenumber dispersion error will produce a more accurate numerical solution in the long-time seismic wave simulation. Thus, how to reduce the low-wavenumber dispersion error becomes a crucial problem. According to the research into the zero-point position at the dispersion curve for three types of cost function, we found that the more zero points concentrate on the low-wavenumber region, the less the dispersion error. Therefore, the concentration of zero points is a good way to reduce dispersion error, which can be implemented by modified wavenumbers of zero points. Then, we design a Lagrange dual problem with a restriction based on the modified wavenumbers. The requirements for constructing the Lagrange dual problem are the optimization function and restricted condition, where the former is based on the dispersion relation, and the latter comprises the modified wavenumbers. The solution of this optimization problem, calculated by the dual ascent method, affords a less low-wavenumber dispersion error than the solution yielded by the alternating direction method of multipliers (ADMM). The theoretical analysis and numerical modeling suggest that the proposed method is superior to the existing optimal FD coefficients in reducing numerical error accumulation in low-frequency simulation.

Insoluble lipid film mediates transfer of soluble saccharides from the sea to the atmosphere: the role of hydrogen bonding

Abstract. Saccharides are a large portion of organic matter in sea spray aerosol (SSA). Although they can affect climate-related properties of SSA, the mechanism through which saccharides are transferred from bulk seawater to the ocean surface and ultimately into SSA is still debated. Here, the transfer of small soluble saccharides was validated using a controlled plunging jet sea spray aerosol generator to better understand the wide range of particle properties produced by natural seawater mixed with model organic species, glucose and trehalose. We showed that both soluble saccharides can promote the production of SSA particles, and the presence of trehalose could increase the SSA number concentration by 49.4 %. Conversely, the role of the insoluble fatty acid film on the seawater surface greatly reduced the production of SSA. The resulting inorganic–organic mixed particles identified by the transmission electron microscope (TEM) showed typical core–shell morphology. A Langmuir model was used to parameterize the adsorption and distribution of saccharide into SSA across the bubble surface, while infrared reflection–absorption spectroscopy (IRRAS) combined with Langmuir isotherms was undertaken to examine the effects of aqueous subphase soluble saccharides with various concentrations on the phase behavior, structure, and ordering of insoluble lipid monolayers adsorbed at the air/water interface. We found that the adsorption of glucose and trehalose on the fatty acid monolayer led to the expansion of the mean molecular area. Saccharide–lipid interactions increased with increasing complexity of the saccharide in the order of glucose &lt; trehalose. In a seawater solution, the effects of dissolved saccharides on the ordering and organization of fatty acid chains were muted. The enhancement of the carbonyl band to the low wavenumber region implied that soluble saccharides can form new hydrogen bonds with fatty acid molecules by displacing large amounts of water near the polar headgroups of fatty acids. Our results indicate that the interaction between soluble saccharides and insoluble fatty acid molecules through hydrogen bonds is an important component of the sea–air transfer mechanism of saccharides.

Elucidating l-tyrosine crystal phase transitions by Raman spectroscopy and ab initio calculations

We report here the analysis of the vibrational properties of the l-tyrosine crystal by means of Raman spectroscopy, as well as DFT calculations. The structural stability of the sample was also investigated under high pressure. Single crystals were obtained by the slow solvent evaporation technique. X-ray diffraction experiments were performed at ambient pressure and confirmed the crystalline structure. Simulations of tyrosine dimers allowed us to know some lattice modes. Raman spectra were acquired under ambient conditions and confirmed by ab initio calculations. The classification of the Raman modes is presented and as will be shown, the theoretical results agree with the experimental data. In addition, high pressure Raman spectra were measured from ambient pressure up to 5.9 GPa. The pressure-dependent studies showed that this sample undergoes two phase transitions, at approximately 2 GPa and 3.6 GPa. The transition at 2 GPa is characterized by change of bands in the low-wavenumber region of the spectrum and splitting of a mode associated with torsion of NCCC and rocking of NH3. In the phase transition at 3.6 GPa, changes in the lattice modes and variation of dω/dP for modes between 300 and 450 cm−1 are observed. The observed transitions were reversible when the system brought back to ambient pressure. This study is the first on the crystal of the amino acid l-tyrosine subjected to high pressures, allowing the observation and understanding of the structural and vibrational behavior under these conditions, possibly expanding the possibilities of using this material.

Tailored mesoporous γ-WO3 nanoplates: unraveling their potential for highly sensitive NH3 detection and efficient photocatalysis.

Herein, the monoclinic phase of tungsten oxide (γ-WO3) was successfully obtained after annealing hydrothermally synthesised WO3 powder at 500 °C. As per the result obtained from the N2 adsorption-desorption isotherm, the material has been identified as mesoporous with a specific surface area of 3.71 m2 g-1 from BET (Brunauer-Emmett-Teller) analysis. Moreover, the average pore size (49.52 nm) and volume (0.050 cm3 g-1) were also determined by the BJH (Barrett-Joyner-Halenda) method. FE-SEM (field emission scanning electron microscopy) and HR-TEM (high resolution transmission electron microscopy) have confirmed the formation of nanoplates with an average diameter of approximately 274 nm. Raman spectroscopy has shown peaks at the lower wavenumber region (270 cm-1 and 326 cm-1) and the higher wavenumber region (713 cm-1 and 806 cm-1) for O-W-O bending modes and stretching modes, respectively. The combined effect of relative humidity (RH-11%-RH-95%-RH-11%) and NH3 (150 ppm, 300 ppm, 450 ppm, 600 ppm, 700 ppm, and 800 ppm) was investigated in this reported work. The synthesised γ-WO3 has shown highly responsive behaviour for humidity of 96.5% (RH-11%-95%) and NH3 sensing (under humidity) of 97.4% (RH-11%-95% with 800 ppm NH3). The response and recovery time were calculated as 15 s and 52 s, and 16 s and 54 s for humidity, and NH3 under humidity, respectively. The experimental findings demonstrated that the resistance of the sensor depends on the concentration of NH3 and humidity. Moreover, γ-WO3 has been investigated as a promising catalyst for the dye degradation of methylene blue (MB) with a degradation efficiency of 72.82% and methyl orange (MO) with a degradation efficiency of 53.84% under visible light exposure. This dye degradation occurred within 160 min in the presence of a catalyst under visible light irradiation.

A family of spatio-temporal optimized finite difference schemes with adaptive dispersion and critical-adaptive dissipation for compressible flows

A numerical scheme with good dissipation and dispersion properties is essential for simulations of complex compressible flows in resolving small-scale structures and capturing discontinuities. Although a sufficient numerical dissipation benefits the shock-wave capturing, the fine scales in smooth regions are dissipated either. In this work, a framework to construct arbitrarily high-order spatio-temporal optimized finite difference schemes with adaptive dispersion and critical-adaptive dissipation is proposed, where the dispersion and dissipation properties are characterized by two free parameters respectively. The proposed scheme can automatically adjust these two free parameters to control the dispersion and dissipation according to the local flow-field properties quantified by the scale sensor. As the first step to optimize the spectral properties of the fully discrete scheme, the total dispersion and dissipation errors induced by spatio-temporal discretization are studied. Then, the dispersion property is optimized by a new integrated error function devised for fully discrete scheme. To improve the precision of prediction, the scale sensor employed to quantify the local scaled wavenumber of flow fields is optimized in wavenumber space. Furthermore, a modified dispersion-dissipation condition is developed to characterize the relationship between the total dispersion and dissipation errors. Building upon the optimized scale sensor and modified dispersion-dissipation condition, the critical-adaptive dissipation parameter is obtained, which keeps the numerical dissipation as low as possible to resolve more small-scale structures in the low-wavenumber region and introduces sufficient dissipation to capture strong discontinuities successfully. Moreover, the adaptive dispersion parameter related to the local wavenumber and Courant number is obtained to reduce the total dispersion error significantly. Meanwhile, the critical-adaptive dissipation surface and adaptive dispersion surface are constructed for different Courant number utilized in actual flow simulations, which improves the spectral properties of the proposed scheme. Finally, some benchmark cases involving strong discontinuities and multi-scale structures are employed to verify the attractive performance of the proposed scheme.

Signature of weak-antilocalization in sputtered topological insulator Bi2Se3 thin films with varying thickness

We report a low-temperature magneto transport study of Bi2Se3 thin films of different thicknesses (40, 80 and 160 nm), deposited on sapphire (0001) substrates, using radio frequency magnetron sputtering technique. The high-resolution x-ray diffraction measurements revealed the growth of rhombohedral c-axis {0003n} oriented Bi2Se3 films on sapphire (0001). Vibrational modes of Bi2Se3 thin films were obtained in the low wavenumber region using Raman spectroscopy. The surface roughness of sputtered Bi2Se3 thin films on sapphire (0001) substrates were obtained to be ~ 2.26–6.45 nm. The chemical and electronic state of the deposited Bi2Se3 was confirmed by X-ray photoelectron spectroscopy and it showed the formation of Bi2Se3 compound. Resistivity versus temperature measurements show the metallic nature of Bi2Se3 films and a slight up-turn transition in resistivity at lower temperatures < 25 K. The positive magneto-resistance value of Bi2Se3 films measured at low temperatures (2–100 K) confirmed the gapless topological surface states in Bi2Se3 thin films. The quantum correction to the magnetoconductivity of thin films in low magnetic field is done by employing Hikami–Larkin–Nagaoka theory and the calculated value of coefficient ‘α’ (defining number of conduction channels) was found to be 0.65, 0.83 and 1.56 for film thickness of 40, 80 and 160 nm, respectively. These observations indicate that the top and bottom surface states are coupled with the bulk states and the conduction mechanism in Bi2Se3 thin films varied with the film thicknesses.

Raman Optical Activity of N-Acetyl-L-Cysteine in Water and in Methanol: The "Clusters-in-a-Liquid" Model and ab Initio Molecular Dynamics Simulations.

Raman and Raman Optical Activity (ROA) spectra of N-acetyl-L-cysteine (NALC), a flexible chiral molecule, were measured in water and in methanol to evaluate the solvent effects. Two different solvation approaches, that is, the DFT based "clusters-in-a-liquid" solvent model and the ab initio molecular dynamics (AIMD) simulations, were applied to simulate the Raman and ROA spectra. Systematic conformational searches were carried out using a recently developed conformational searching tool, CREST, with the inclusion of polarizable continuum model of water and of methanol. The CREST candidates of NALC and the NALC-solvent complexes were re-optimized and their Raman and ROA simulations were done at the B3LYP-D3BJ/def2-TZVP and the B3LYP-aug-cc-pVDZ//cc-pVTZ levels. Also, AIMD simulations, which includes some anharmonic effects and all intermolecular interactions in solution, were performed. By empirically weighting the computed Raman and ROA spectra of each conformer, good agreements with the experimental data were achieved with both approaches, while AIMD offered some improvements in the carbonyl and in the low wavenumber regions over the static DFT approach. The pros and cons of these two different approaches for accounting the solvent effects on Raman and ROA of this flexible chiral system will also be discussed.