Local chain dynamics of a model polycarbonate near glass transition temperature: A molecular dynamics simulation

Constant pressure constant temperature molecular dynamics method is employed to investigate the atomistic scale dynamics of a model Bisphenol A polycarbonate in the vicinity of its glass transition temperature. First, the glass transition temperature and the thermal expansion coefficients of the polymer are predicted by performing simulations at different temperatures. To explore the significance of different modes of motion, various types of time correlation functions are utilized in analyzing the trajectories. In these nanosecond scale simulations, the motion of the chain segments is found to be highly localized with little reorientation of the vectors representing these segments. Detailed analysis of trajectories and the correlation functions of the backbone dihedrals and side methyl groups indicates that they exhibit numerous conformational transitions. The activation energies of the conformational transitions obtained from the simulation are generally larger than the potential barriers for the rotations of these dihedrals, however, both show the same trend. We also have estimated the phenylene ring flip activation energy as 12.6 kcal/mol and the flip frequency as 0.77 MHz at 300 K. These values fall either fall within the range determined by various NMR spectroscopy experiments or slightly out of the range. The study shows that the conformational transitions between the adjacent dihedrals are strongly correlated. Three basic cooperative modes are identified from the simulation. They are: a positive synchronous rotation of two phenylene rings, a negative synchronous rotation of two phenylene rings, and a carbonate group rotation. Above the glass transition temperature, the large scale cooperative motions become much more significant.     

FT‐Raman and FT‐IR spectral and quantum chemical studies on some flavonoid derivatives: Baicalein and Naringenin

In this study, the experimental and theoretical results on the molecular structures of some flavonoid derivatives (Baicalein and Naringenin) are presented. The FT‐IR and FT‐Raman spectra of the compounds have been recorded together for the first time between 4000–400 cm⁻¹ and 3500–5 cm⁻¹ regions, respectively. The molecular geometry and vibrational wavenumbers of the compounds have been also calculated in their ground states by using ab initio HF and DFT/B3LYP functional with 6‐31G(d,p) basis set used in calculations. The calculations were utilized to the C₁ symmetries of the molecules. All calculations were performed with Gaussian 98 software. The obtained vibrational wavenumbers and optimized geometric parameters were seen to be in good agreement with the experimental data. Scale factors have been used in order to compare how the calculated and experimental data are in agreement. Theoretical infrared intensities were also reported. Copyright © 2008 John Wiley & Sons, Ltd.     

Theoretical and experimental study on metal(II) halide complexes of 1,3-bis(4-pyridyl)propane

We report the results of detailed experimental and theoretical studies on the molecular structure and vibrational spectra of metal(II) halide complexes of 1,3-bis(4-pyridyl)propane [M(N₂C₁₃H₁₄)X₂, where M represents Zn or Hg, and X represents Cl, Br, or I]. The FT–infrared spectra (FT-IR) and FT-Raman spectra of the metal complexes of the 1,3-bis(4-pyridyl)propane molecule in the powder form were recorded between the 400–4000 and 5–3500 cm^?1 regions, respectively. The molecular geometry and vibrational frequencies of the metal complexes of 1,3-bis(4-pyridyl)propane in the ground state were calculated using density functional theory (B3LYP functional) with LANL2DZ and SDD as basis sets. The total energy distributions (TED) among the symmetry coordinates of the normal modes were computed for the low-energy structure of the molecules. Complete vibrational assignments based on the calculated TED values are given.     

Effects of various competing ligands on the kinetics of trace metal complexes of Laurentian Fulvic Acid in model solutions and natural waters

The objective of this work was to study the effects of the following Ligands: Chelex-100, Dowex MAC-3 and Dowex 50WX-8 using Competing Ligand Exchange Method. This objective was achieved by investigating complex dissociation kinetics of trace metals: Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Mn(II) and Pb(II) of a well-characterized Laurentian Fulvic Acid (LFA) in model solutions and in a natural waters of Lake Heva (Québec, Canada). The effects of variation in the competing ligands (including their quantities) on the complex dissociation kinetics were quantitatively characterized by their first-order dissociation rate coefficients. The kinetic lability of the metal complexes varied with the metal-to-LFA ratio, as expected from the theory of metal complexes of the chemically and physically heterogeneous complexants, LFA. The general trend in the metal-binding by the above competing ligands was: Dowex 50WX-8 > Chelex-100 > Dowex MAC-3. However, no difference was found between the Dowex 50WX-8 and Chelex-100 for Cd(II), Zn(II), and Co(II). The results revealed the importance of the quantity of Chelex-100 as a competing ligand in the metal(II)-LFA complexation, on the dissociation kinetics of these complexes in model solutions. By developing Competing Ligand Exchange Method as an analytical technique, for studying the relative affinities of the above competing ligands for metals complexation in natural waters this work has made a substantial contribution to analytical chemistry.     

Interference of Nonstandard Interactions with Standard Model in $${B^0} \to {\pi ^0}\bar vv$$, $$B_c^ - \to {D^ - }\bar vv$$Bc−→D−v¯v and $$\bar B_s^0 \to {K^0}\bar vv$$B¯s0→K0v¯v Decays

We study the contributions of nonstandard neutrino interactions (NSI) to the rare decays of pseudoscalar mesons involving neutrinos in the final state \({B^0} \to {\pi ^0}\bar vv\), \(B_c^ - \to {D^ - }\bar vv\) and \(\bar B_s^0 \to {\bar K^0}\bar vv\), It is pointed that dominant contribution comes from the interference between standard model and nonstandard interaction We predict limits on NSIs free parameter ε ^uL _ττ and compare them with experimental data. We further compare our results with perturbative QCD (pQCD) and QCD results for these reactions.     

Modulating opto-electronic and magnetic responses of Mo- and Zn-adsorbed LiNbO3 (1 1 1) surface for advanced energy harvesting applications: A comprehensive study

This study aimed to comprehensively investigate the optoelectronic and magnetic properties of Mo, Zn/LiNbO₃ (1 1 1) material. The primary objectives were to understand the potential for manipulating the material's magnetism and to elucidate the origin of spin-polarized states and magnetic moments, particularly with respect to the unpaired d orbitals of Nb, Mo, and Zn atoms. To achieve these objectives, we employed the Pardew–Burke–Ernzerhof (PBE) method within the Generalized Gradient Approximation (GGA + U) framework. This computational approach allowed us to examine the optoelectronic and magnetic characteristics of the material in detail. Our research yielded several key findings that enhance our understanding of Mo, Zn/LiNbO₃ (1 1 1) material. We observed a modest improvement in the material's absorption capacity within the visible spectrum, accompanied by a discernible red-shift. Notably, our study involved the calculation of the dielectric function and refractive constant of the material, revealing a strong correlation between absorption trends and the dielectric constant. Furthermore, our investigation uncovered that Mo, Zn/LiNbO₃ (1 1 1) exhibits distinct conduction and valence bands, with p and d orbitals predominantly contributing to each, respectively. The energy gap of the material falls within a range of 0.30–1.04 eV. A particularly significant finding was the narrower band gap of Mo, Zn/LiNbO₃ (1 1 1) material, which can be attributed to the superposition of Mo-d and Zn-p orbit energy levels with O-p orbit energy levels, ultimately forming a covalent bond. Importantly, our research demonstrated the material's heightened optical absorption within the visible spectrum, suggesting its suitability for various photonic and optoelectronic applications. Additionally, we calculated a wide range of optical characteristics, including the dielectric function, absorption coefficient, energy loss, reflectivity, refractive index, extinction coefficient, and optical conductivity, providing a comprehensive assessment of the material's optical properties.     

Superposition Coding with Unequal Error Protection for the Uplink of Overloaded DS-CDMA System

The overloaded CDMA schemes exploited in direct sequence CDMA (DS-CDMA) systems are mainly to accommodate a greater number of users than the available spreading factor N. In this paper, a superposition coding CDMA (SPC-CDMA) with unequal error protection (UEP) is proposed as one of the overloaded CDMA schemes for the next generation mobile communication systems. It exploits the available power control in most base stations to adapt the transmitted power of active users in the uplink channel. In this scheme, the active users are divided into G groups and each group consists of K users. The K users share the same spreading sequence and are distinguished by different received power levels. At the receiver side, the system first performs despreading for group detection followed by multiuser receiver to estimate the K user signals in each group. It is shown through simulations that better performance are achieved compared to the conventional DS-CDMA and existing overloaded collaborative spreading CDMA (CS-CDMA) schemes, in additive white Gaussian noise (AWGN) and fading channels. Hence, the proposed scheme maximizes the system capacity K-fold compared to conventional DS-CDMA system without requiring extra spreading codes, with average signal to noise ratio (SNR) cost of only 1dB and 2 dB over AWGN and fading channels respectively at BER of 10^?3. On the other hand, for the same N, K and power constraints, SPC-CDMA scheme achieves twofold increase in data rate with 0.7 and 4 dB gains over AWGN and fading channels respectively, compared with overloaded CS-CDMA scheme in the same system capacity. In addition, the proposed scheme can also attain different levels of UEP for different users?? requirements by adjusting their fractions of transmitted powers.     

New insights into water splitting at mesoporous α-Fe2O3 films: a study by modulated transmittance and impedance spectroscopies

Thin mesoporous films of α-Fe(2)O(3) have been prepared on conducting glass substrates using layer-by-layer self-assembly of ca. 4 nm hydrous oxide nanoparticles followed by calcining. The electrodes were used to study the oxygen evolution reaction (OER) in the dark and under illumination using in situ potential-modulated absorption spectroscopy (PMAS) and light-modulated absorption spectroscopy (LMAS) combined with impedance spectroscopy. Formation of surface-bound higher-valent iron species (or "surface trapped holes") was deduced from the PMAS spectra measured in the OER onset region. Similar LMAS spectra were obtained at more negative potentials in the onset region of photoelectrochemical OER, indicating involvement of the same intermediates. The impedance response of the mesoporous α-Fe(2)O(3) electrodes exhibits characteristic transmission line behavior that is attributed to slow hopping of holes, probably between surface iron species. Frequency-resolved PMAS and LMAS measurements revealed slow relaxation behavior that can be related to the impedance response and that indicates that the lifetime of the intermediates (or trapped holes) involved in the OER is remarkably long.     

Characterization of brush type discharge electrodes and impact of enhanced corona discharge on operation of electrostatic precipitators

This project presents the results of investigation of current/voltage characteristics of brush type discharge electrodes (BTDE) in tube type electrostatic precipitators and the effect on operation. Experimental investigations were conducted with discharge electrodes of different wire diameter and different brush diameter. The effect of electrode geometry on current/voltage behavior was recorded. Corona current with brush type discharge electrodes was modeled and compared with experimental data. Brush type discharge electrodes produce an enhanced corona current compared with wire type discharge electrodes. Limited enhanced corona has improving effect on collection efficiency. An adjusted correlation was therefore deduced from experimentally obtained current/voltage data with BTDE.     

Vibrations of FGM thin cylindrical shells with exponential volume fraction law

In this paper, the influence of an exponential volume fraction law on the vibration frequencies of thin functionally graded cylindrical shells is studied. Material properties in the shell thickness direction are graded in accordance with the exponential law. Expressions for the strain-displacement and curvature-displacement relationships are taken from Love＇s thin shell theory. The Rayleigh-Ritz approach is used to derive the shell eigenfrequency equation. Axial modal dependence is assumed in the characteristic beam functions. Natural frequencies of the shells are observed to be dependent on the constituent volume fractions. The results are compared with those available in the literature for the validity of the present methodology.