Starch-Assisted Synthesis of Bi2S3 Nanoparticles for Enhanced Dielectric and Antibacterial Applications.

Starch [(C6H10O5) n ]-stabilized bismuth sulfide (Bi2S3) nanoparticles (NPs) were synthesized in a single-pot reaction using bismuth nitrate pentahydrate (Bi(NO3)3·5H2O) and sodium sulfide (Na2S) as precursors. Bi2S3 NPs were stable over time and a wide band gap of 2.86 eV was observed. The capping of starch on the Bi2S3 NPs prevents them from agglomeration and provides regular uniform shapes. The synthesized Bi2S3 NPs were quasispherical, and the measured average particle size was ∼11 nm. The NPs are crystalline with an orthorhombic structure as determined by powder X-ray diffraction and transmission electron microscopy. The existence and interaction of starch on the NP's surface were analyzed using circular dichroism. Impedance spectroscopy was used to measure the electronic behavior of Bi2S3 NPs at various temperatures and frequencies. The dielectric measurements on the NPs show high dielectric polarizations. Furthermore, it was observed that the synthesized Bi2S3 NPs inhibited bacterial strains (Bacillus subtilis, Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus) and demonstrated substantial antibacterial activity.

Pressure-Induced Amorphization of Diisopropylammonium Perchlorate Studied by Raman Spectroscopy and X-ray Diffraction.

Diisopropylammonium salts have drawn attention in recent years due to their room-temperature ferroelectric properties. Triclinic diisopropylammonium perchlorate (DIPAP) exhibits ferroelectricity at room temperature. We have carried out density functional theory calculations to assign the phonon modes in DIPAP. High-pressure Raman spectra of DIPAP are recorded up to ∼3 GPa. Discontinuity in the NH2 bending and stretching mode frequencies and the appearance of new bands at 0.7 GPa suggest a phase transition by a rearrangement in the hydrogen network. Broadening of lattice modes at 1.3-1.7 GPa indicates a loss of crystalline nature above 1.7 GPa. High-pressure synchrotron X-ray diffraction of DIPAP shows an isostructural phase transition at 0.6 GPa and confirms amorphization at 1.5 GPa that may lead to a loss of ferroelectricity above this pressure. The ambient phase becomes reversible after releasing the pressure. The bulk modulus of DIPAP is determined to be 16.5 GPa.

Optimization of a spatial light modulator driven by digital video interface graphics to generate holographic optical traps.

We propose a method to optimize spatial light modulators (SLMs) driven by digital video interface graphics in a holographic optical tweezers system. A method analogous to that used to optimize LCD televisions is used to optimize the properties of the graphics card through a diffraction-based experiment and develop a lookup table for the SLM. The optimization allows the SLM to function with its full phase modulation depth with improved diffraction efficiency. Further, we propose a simple and robust method to correct for the spatially varying phase response of the SLM to enhance its diffraction efficiency. The optimization results in an improvement of uniformity in the intensity and quality of the trap spots.

Perceptible isotopic effect in 3D-framework of α-glycine at low temperatures.

Glycine, the most fundamental amino acid, albeit studied for many decades, has kept researchers captivated with interesting structural variations relevant to important biological, astrophysical and technological applications. We report here a noticeable effect of deuteration on the three dimensional hydrogen bonding network of α-glycine using low temperature infrared absorption studies in a wide spectral range, corroborated with Raman scattering studies. These systematic studies in the range 300-4.2 K have demonstrated a relatively compact assembly of glycine molecules in the three dimensional bilayered structure of hydrogenated glycine (gly-h) at low temperatures. This is inferred from a remarkable temperature effect in the weak intra-bilayer hydrogen bond ~ along the b-axis, which strengthens upon cooling. A pronounced increase in the intensity of NH3 torsional and NH stretching modes has been observed. This is accompanied with a large rate of stiffening and softening respectively of these modes upon cooling and a change in slope across 210 K and 80 K. In contrast, the D---O hydrogen bond lengths in fully deuterated isotope (gly-d), as estimated using empirical correlation, show that the weak intra-bilayer hydrogen bond is not strengthened upon cooling down to 180 K, whereas the stronger intra-layer hydrogen bonds in the ac-plane become further strong. The ND3 torsional vibrations show no temperature effect. This implies a relatively stable two dimensional layered structure formed by strongly hydrogen bonded glycine sheets in the ac-plane. Below 180 K, similar qualitative trends have been obtained for the hydrogen bond lengths in the two isotopes. In addition, temperature induced variation of the characteristic "indicator" band of zwitterionic gly-h and gly-d has also been reported.

New High Pressure Phases of Energetic Material TEX: Evidence from Raman Spectroscopy, X-ray Diffraction, and First-Principles Calculations.

Samples of energetic material TEX (C6H6N4O8) are studied using Raman spectroscopy and X-ray diffraction (XRD) up to 27 GPa pressure. There are clear changes in the Raman spectra and XRD patterns around 2 GPa related to a conformational change in the TEX molecule, and a phase transformation above 11 GPa. The molecular structures and vibrational frequencies of TEX are calculated by density functional theory based Gaussian 09W and CASTEP programs. The computed frequencies compare well with Raman spectroscopic results. Mode assignments are carried out using the vibrational energy distribution analysis program and are also visualized in the Materials Studio package. Raman spectra of the high pressure phases indicate that the sensitivity of these phases is more than that of the ambient phase.

Vibrational spectroscopic and computational studies on diisopropylammonium bromide.

Diisopropylammonium bromide (DIPAB) can be crystallized either in an orthorhombic (P212121) or in a monoclinic (P21) structure at room temperature depending on synthesis conditions. The non-polar orthorhombic structure exhibits a subtle, irreversible transformation into the ferroelectric monoclinic-II (m-II) phase above ~421K. At a slightly higher temperature of 426K this m-II (P21) phase reversibly transforms into a disordered, paraelectric monoclinic-I (P21/m) structure. We synthesized DIPAB in the orthorhombic structure, heated it to obtain the m-II phase and carried out a systematic study of their Raman and IR spectra. We obtained the phonon irreducible representations from factor group analysis of the orthorhombic and m-II structures based on the reported structural information. DIPAB is an organic molecular crystal, and the vibrational spectra in the intramolecular region (200-3500cm-1) of the two different phases are identical to each other, indicating weak inter-molecular interactions in both crystalline structures. In the low wavenumber region (10-150cm-1) the Raman spectra of the two phases are different due to their sensitivity to molecular environment. We also carried out first principles calculations using Gaussian 09 and CASTEP codes to analyze the vibrational frequencies. Mode assignments were facilitated by isolated molecule calculations that are also in good agreement with intramolecular vibrations, whereas CASTEP (solid state) results could explain the external modes.

Phase Transformation, Vibrational and Electronic Properties of K2Ce(PO4)2: A Combined Experimental and Theoretical Study.

Herein we report the high-temperature crystal chemistry of K2Ce(PO4)2 as observed from a joint in situ variable-temperature X-ray diffraction (XRD) and Raman spectroscopy as well as ab initio density functional theory (DFT) calculations. These studies revealed that the ambient-temperature monoclinic (P21/n) phase reversibly transforms to a tetragonal (I41/amd) structure at higher temperature. Also, from the experimental and theoretical calculations, a possible existence of an orthorhombic (Imma) structure with almost zero orthorhombicity is predicted which is closely related to tetragonal K2Ce(PO4)2. The high-temperature tetragonal phase reverts back to ambient monoclinic phase at much lower temperature in the cooling cycle compared to that observed at the heating cycle. XRD studies revealed the transition is accompanied by volume expansion of about 14.4%. The lower packing density of the high-temperature phase is reflected in its significantly lower thermal expansion coefficient (αV = 3.83 × 10-6 K-1) compared to that in ambient monoclinic phase (αV = 41.30 × 10-6 K-1). The coexistences of low- and high-temperature phases, large volume discontinuity in transition, and large hysteresis of transition temperature in heating and cooling cycles, as well as drastically different structural arrangement are in accordance with the first-order reconstructive nature of the transition. Temperature-dependent Raman spectra indicate significant changes around 783 K attributable to the phase transition. In situ low-temperature XRD, neutron diffraction, and Raman spectroscopic studies revealed no structural transition below ambient temperature. Raman mode frequencies, temperature coefficients, and reduced temperature coefficients for both monoclinic and tetragonal phases of K2Ce(PO4)2 have been obtained. Several lattice and external modes of rigid PO4 units are found to be strongly anharmonic. The observed phase transition and structures as well as vibrational properties of both ambient- and high-temperature phases were complimented by DFT calculations. The optical absorption studies on monoclinic phase indicated a band gap of about 2.46 eV. The electronic structure calculations on ambient-temperature monoclinic and high-temperature phases were also carried out.

Temperature dependent structural, vibrational and magnetic properties of K3Gd5(PO4)6.

Herein we report the evolution of the crystal structure of K3Gd5(PO4)6 in the temperature range from 20 K to 1073 K, as observed from variable temperature X-ray diffraction and Raman spectroscopic studies. K3Gd5(PO4)6 has an open tunnel containing a three dimensional structure built by [Gd5(PO4)6]3- ions which in turn are formed of PO4 tetrahedra and GdOn (n = 8 and 9) polyhedra. The empty tunnels in the structure are occupied by K+ ions and maintain charge neutrality in the lattice. Evolution of unit cell parameters with temperature shows a systematic increase with temperature. The average axial thermal expansion coefficients between 20 K and 1073 K are: αa = 10.6 × 10-6 K-1, αb = 5.5 × 10-6 K-1 and αc = 16.4 × 10-6 K-1. The evolution of distortion indices of the various coordination polyhedra with temperature indicates a gradual decrease with increasing temperature, while those of Gd2O9 and K2O8 polyhedra show opposite trends. The overall anisotropy of the lattice thermal expansion is found to be controlled largely by the effect of temperature on GdOn polyhedra and their linkages. Temperature dependent Raman spectroscopic studies indicated that the intensities and wavenumbers of most of the Raman modes decrease continuously with increasing temperature. Anharmonic analyses of Raman modes indicated that the lattice, rigid translation and librational modes have larger contributions towards thermal expansion of K3Gd5(PO4)6 compared to high frequency internal modes. The temperature and field dependent magnetic measurements indicated no long range ordering down to 2 K and the observed effective magnetic moment per Gd3+ ion and the Weiss constant are 7.91 µB and 0.38 K, respectively.

Structural and Thermal Properties of BaTe2O6: Combined Variable-Temperature Synchrotron X-ray Diffraction, Raman Spectroscopy, and ab Initio Calculations.

Variable-temperature Raman spectroscopic and synchrotron X-ray diffraction studies were performed on BaTe2O6 (orthorhombic, space group: Cmcm), a mixed-valence tellurium compound with a layered structure, to understand structural stability and anharmonicity of phonons. The structural and vibrational studies indicate no phase transition in it over a wider range of temperature (20 to 853 K). The structure shows anisotropic expansion with coefficients of thermal expansion in the order αb ≫ αa > αc, which was attributed to the anisotropy in bonding and structure of BaTe2O6. Temperature evolution of Raman modes of BaTe2O6 indicated a smooth decreasing trend in mode frequencies with increasing temperature, while the full width at half-maximum (fwhm) of all modes systematically increases due to a rise in phonon scattering processes. With the use of our earlier reported isothermal mode Grüneisen parameters, thermal properties such as thermal expansion coefficient and molar specific heat are calculated. The pure anharmonic (explicit) and quasiharmonic (implicit) contribution to the total anharmonicity is delineated and compared. The temperature dependence of phonon mode frequencies and their fwhm values are analyzed by anharmonicity models, and the dominating anharmonic phonon scattering mechanism is concluded in BaTe2O6. In addition to the lattice modes, several external modes of TeOn (n = 5, 6) are found to be strongly anharmonic. The ab initio electronic structure calculations indicated BaTe2O6 is a direct band gap semiconductor with gap energy of ∼2.1 eV. Oxygen orbitals, namely, O-2p states in the valence band maximum and the sp-hybridized states in the conduction band minimum, are mainly involved in the electronic transitions. In addition a number of electronic transitions are predicted by the electronic structure calculations. Experimental photoluminescence results are adequately explained by the ab initio calculations. Further details of the structural and vibrational properties are explained in the manuscript.

Surfactant assisted control on optical, fluorescence and phonon lifetime in α-Bi2O3 microrods.

We report preparation of pure and surfactant added α-Bi2O3 microrods through simple chemical method at moderate temperature. Cetyltrimethyl ammonium bromide (CTAB) is used as a surfactant. X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy, Raman spectroscopy, UV-Vis absorption and photoluminescence (PL) measurements were carried out to understand the effect of surfactant (CTAB) on structural, phonon and optical properties of the prepared material. It is observed that the crystallite size, optical band gap and the structural defects (oxygen vacancies) decreases due to the effect of surfactant. Raman spectral studies exhibit various phonon modes of Bi2O3 and also decrease in the FWHM of the phonon modes is observed after the addition of CTAB.

Temperature and Pressure Dependent Phase Transitions of ß'-LiZr2(PO4)3 Studied by Raman Spectroscopy.

LiZr2(PO4)3 (LZP) belongs to the NASICON family of compounds whose ionic conductivity can be tuned by substitution of different cations or by increasing the temperature or pressure. Besides its conductivity, thermal and electrochemical stability makes it useful as a cathode material for lithium-ion energy storage devices. Temperature dependent Raman spectroscopic studies were carried out on the monoclinic (ß') phase of LZP in the temperature range 298-853 K. A reversible structural phase transition driven by disorder in lithium sites is observed at 603 K. The spectral data enable an understanding of dynamics of the mobile Li ion and PO4 internal modes across the orthorhombic structural phase transition. On the basis of these studies, a reported change in the conductivity around 600 K is explained. High pressure Raman spectroscopic measurements on ß'-LiZr2(PO4)3 reveal the onset of a structural phase transformation at 3.8 GPa and amorphization above 10 GPa. On decompression from 26 GPa, the amorphous phase remains unchanged, indicating irreversible nature of pressure-induced amorphization. Three low frequency Raman modes at 100, 124, and 144 cm(-1), which soften with an increase in pressure could be the driving force for the phase transition at 3.8 GPa. Pressure-induced phase transition prior to amorphization in ß'-LiZr2(PO4)3 could be due to collapse of Zr-O-P bond angles. Pressure-induced amorphization in this compound might be due to kinetic hindrance of equilibrium decomposition.

Comparative Raman spectroscopic study of phase stability and anharmonic effects in AZr2(PO4)3 (A=K, Rb and Cs).

AZr2(PO4)3 (A=Na, K, Rb, Cs) are a set of framework structured compounds that exhibit tunable ultralow thermal expansion over the wide temperature range of 293-1273K. We report a systematic Raman spectroscopic investigation on AZr2(PO4)3 (A=K, Rb and Cs) compounds as a function of temperature in the range 80-860K and pressures of up to 32GPa. To get insight into the thermal expansion property, phonon anharmonicity has been investigated by studying the temperature and pressure dependence of Raman peak shifts and line widths and computed bulk modulus. We have compared the phase transition and amorphization pressures of the various members of AZr2(PO4)3 to account for the stability of the ambient rhombohedral phase. We find that unlike most of the anomalous thermal expansion materials, in AZr2(PO4)3 (A=K, Rb and Cs), the phonons that are anharmonic with temperature do not necessarily exhibit anharmonicity with pressure.

High pressure Raman spectroscopy of layered matlockite, PbFCl.

The pressure dependence of various inter- and intra-layer Raman modes has been studied on pristine matlockite compound, PbFCl, up to ~41 GPa. The low-frequency interlayer vibrational modes, A1g(1) and Eg(1), identified as rigid layer modes, exhibit non-monotonic behavior with increasing pressure. They exhibit points of inflexion at ~24 GPa and ~31 GPa respectively, indicating the onset of a subtle instability. The emergence of a new Raman mode (~181 cm(-1)) at ~24 GPa and a sudden large increase in the intensity of the A1g(1) mode signify the occurrence of a symmetry lowering structural transition of the parent tetragonal phase with enhanced interlayer coupling. Two more modes appear at higher pressures (~33 GPa) at frequencies below the A1g(1) mode and are ascribed to a monoclinically distorted phase (space group P21/m). High pressure x-ray diffraction studies performed up to ~47 GPa confirm the occurrence of the structural transitions with decreasing crystal symmetry. These observations are consistent with a picture in which the structural distortion involves destabilization of the tetragonal unit cell following a gradual change in the bonding nature from layer-like (2D) to non-layer like (3D) involving the Cl-bilayers along the c direction.

Polymorphism of dense, hot oxygen.

The phase diagram and polymorphism of oxygen at high pressures and temperatures are of great interest to condensed matter and earth science. X-ray diffraction and Raman spectroscopy of oxygen using laser and resistively heated diamond anvil cells reveal that the molecular high-pressure phase ε-O(2), which consists of (O(2))(4) clusters, reversibly transforms in the pressure range of 44 to 90 GPa and temperatures near 1000 K to a new phase with higher symmetry. The data suggest that this new phase (η') is isostructural to a phase η reported previously at lower pressures and temperatures, but differs from it in the P-T range of stability and type of intermolecular association. The melting curve increases monotonically up to the maximum pressures studied (∼60 GPa). The structure factor of the fluid measured as a function of pressure to 58 GPa shows continuous changes toward molecular dissociation.

Gold nanorods with finely tunable longitudinal surface plasmon resonance as SERS substrates.

Advances in nanophotonics have shown the potential of colloidal metal nanoparticles with sharp tips, such as rods, to focalize plasmonic electromagnetic fields. We report on the synthesis of Au nanorods via a seed mediated approach and the influence of silver ions on the aspect ratio of the Au nanorods. The longitudinal surface plasmon resonance (LSPR) of the Au nanorods was successfully tuned with the concentration of silver ions. The surface enhanced Raman scattering (SERS) effect of 2-aminothiophenol (2-ATP) as a probe molecule on Au nanorods was systematically studied by varying the longitudinal surface plasmon resonance of the nanorods. The highest electromagnetic enhancement was observed when the longitudinal surface plasmon resonance of the Au nanorods overlapped with the laser excitation wavelength. The variation of the SERS enhancement factor with the longitudinal surface plasmon resonance and laser excitation lines is also discussed in detail.