Microwave dielectric absorption studies of hydrogen bonded polar binary mixtures of isobutanol with tertiary butyl amine

The dielectric behaviour of polar liquids like isobutanol, tertiary butyl amine and their equimolar binary mixture in nonpolar solvent benzene is studied in the microwave frequency range using the cavity perturbation technique at 6.218?GHz (J band), 9.880?GHz (X band), 16.331?GHz (P band) and 24.951?GHz (K band). Hamiltonian quantum mechanical calculations such as AM1, PM3 and MNDO optimized converged geometry operation is performed on isobutanol, tertiary butyl amine and their equimolar binary mixtures using Argus lab chemical modelling software, 2004. Dipole moments of the binary mixtures are calculated from the dielectric data using Higasi's method, and compared with the theoretical Hamiltonian quantum mechanical results. Conformational analysis of the formation of hydrogen bond between the isobutanol and tertiary butyl amine is supported by FT-IR and proton NMR spectra. The average relaxation times are calculated from their respective Cole–Cole plots.     

Dielectric relaxation, thermodynamic and theoretical studies on hydrogen bonded polar binary mixtures of N-methyl aniline with propan-1-ol and isopropyl alcohol

The dielectric relaxation studies on polar binary mixtures of N-methyl aniline with, alcohols, propan-1-ol and isopropyl alcohol have been carried out, at different temperatures and mole fractions, using — LF impedance analyzer, Plunger method and Abbe’s refractometer in radio, microwave and optic frequency regions respectively. Kirkwood effective correlation factor, corrective Kirkwood correlation factor, Bruggeman parameter, relaxation time and thermodynamical parameters are calculated using the experimental data. Conformational analysis of the formation of hydrogen bond in the equi molar binary mixture systems of N-methyl aniline with propan-1-ol and isopropyl alcohol is supported by experimental and theoretical FT-IR values.     

Densities, excess molar volumes and partial molar volumes of the binary mixtures of acetic acid + alkanol (C1–C4) at 298.15 K

Densities (ρ) of the binary mixtures of acetic acid with methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol and butan-2-ol have been measured at temperature 298.15 K and ambient pressure (815 hPa) as a function of composition using an Anton Paar model DMA 4500 oscillating densimeter. The excess molar volume (V_m^E), partial molar volume (V¯_i) and excess partial molar volumes (V¯_i^E) of the binary mixtures were calculated from the density data. The excess molar volumes were correlated with the Redlich−Kister equation. The excess molar volumes are negative for methanol, ethanol, propan-1-ol, propan-2-ol and butan-1-ol. They are positive for butan-2-ol and an inversion of sign in V_m^E is observed for butan-2-ol around 0.9 mol fraction of acetic acid.

The results obtained in this work were interpreted in terms of intermolecular interaction between like and unlike molecules, difference in size and shape of unlike molecules and the steric hindrance caused by increased methylation.     

Dielectric studies of alkyl acrylates with primary alcohols using time domain reflectometry

Binary polar–polar liquid mixtures of alkyl acrylates (methyl acrylate, ethyl acrylate and butyl acrylate) with primary alcohols (propan-1-ol, butan-1-ol and hexan-1-ol) were subjected to dielectric studies at 303?K for different concentrations using time domain reflectometry (TDR) over the frequency range from 10?MHz to 10?GHz. Static permittivity (ε₀) dielectric constant at high frequency (ε_∞) and relaxation time (τ) were found through dielectric measurements for different concentrations of each system. The Bruggeman dielectric factor, Kirkwood correlation factor and the excess inverse relaxation time were determined and discussed to yield information on the molecular interactions of the systems. Deviations from the linearity of various models suggest molecular association through hydrogen bonding between the ?OH group of alcohols and C=O group of esters. The results also show a dependence of dielectric parameters on the alkyl chain length of both the alcohols and esters.     

Dielectric absorption in mixtures of anisole with some primary alcohols at microwave frequency

Dielectric properties of binary mixtures of anisole with methanol (MeOH), 1-propanol (1-PrOH), 1-butanol (1-BuOH) and 1-heptanol (1-HeOH) over an entire concentration range have been studied at a fixed temperature 40°C. The dielectric constant (ε′) and dielectric loss (ε″) of the binary mixtures of polar liquids have been determined at a microwave frequency of 9.1?GHz. The static dielectric permittivity (ε ₀) of the liquid samples was also determined using a precision LCR meter. Determined values of static dielectric permittivity (ε ₀) and dielectric permittivity (ε*) at 9.1?GHz frequency were used to evaluate relaxation time (τ) and high frequency limit dielectric permittivity (ε _∞). Dielectric parameters were interpreted in terms of molecular interaction between the anisole and alcohol molecules.     

Excess permittivity behaviour of some mixtures n-alcohol + alkane: an interpretation of the underlying molecular mechanism

A molecular mechanism is proposed that underlies the macroscopic behaviour of excess dielectric permittivity of some mixtures {n-alcohol?+?alkane} at low (100?kHz) and microwave frequencies (1?GHz). This behaviour has been determined experimentally at 298?K, as a function of molar fraction, for the mixtures {n-hexane?+?(pentan-1-ol, hexan-1-ol or heptan-1-ol)} and {cyclohexane?+?(pentan-1-ol, hexan-1-ol or heptan-1-ol)}. From the magnitudes inherent to the process of dielectric relaxation the results obtained have been explained in terms of the behaviour of thermodynamic magnitudes such as the excess molar enthalpy and the excess molar volume, as well as the consideration that the total dipole moment of a multimere is greater than the sum of all dipole moments of the monomeres in which it can be decomposed (when hydrogen bonds are broken), in agreement with the linear association model of Malecki (LAM). Measurements of the relaxation times for the mixtures under study at various molar fractions using time-domain reflectometry (TDR) (DC–5?GHz) at ambient temperature confirm the considerations that support the proposed interpretation.     

Correlation studies on dielectric and thermodynamic parameters in the binary mixtures of N-methyl aniline and alcohols

The dielectric and thermodynamic studies on polar binary mixtures of N- methyl aniline with alcohols — propan-1-ol and propan-2-ol have been carried out, at different temperatures and mole fractions. LF impedance analyzer, Microwave bench and Abbe’s refractometer are used respectively in radio, microwave (X-Band) and high frequency regions to determine the dielectric data. The experimental data is used to correlate the dielectric and thermodynamic parameters — static permittivity, high frequency permittivity, Kirkwood effective correlation factor, corrective Kirkwood correlation factor, excess permittivity, excess Helmholtz free energy, dipole moment, excessive dipole moment, relaxation time, excess inverse relaxation time and the excess thermodynamic parameters. These parameters are used to interpret the molecular interactions between the molecular species of the liquid mixtures.     

Solvatochromism,Preferential Solvation of 2,3-Bis(Chloromethyl)-1,4-Anthraquinone in Binary Mixtures and the Molecular Recognition Towards <Emphasis Type="Italic">p</Emphasis>-Tert-Butyl-Calix[4]arene

Optical absorption and fluorescence emission spectra of 2,3-bis(chloromethyl)-1,4-anthraquinone (DCMAQ) in single solvents namely, carbon tetrachloride, acetonitrile, chloroform, propan-2-ol and its binary mixtures [carbon tetrachloride/chloroform, chloroform/acetonitrile, chloroform/propan-2-ol] have been investigated. The preferential solvation of DCMAQ in above mixtures has been studied by monitoring the absorption and fluorescence spectra of DCMAQ. The spectral features indicate that DCMAQ is preferentially solvated by CHCl₃ in the above mixtures. This can be elucidated from the local mole fraction, non-linearity in transition energy plot, preferential solvation index (δ _s2) and (f ₂/f ₁) values. Molecular recognition properties of p-tert-butylcalix[4]arene (tBC) to DCMAQ via hydrogen bonding and π–π interaction were sensed successfully on the basis of absorption and fluorescence emission spectroscopies, by which the stoichiometry ratio and the binding constant of the tBC–DCMAQ complex were determined.     

First-principles study of the optical properties of PbFX (X = Cl,Br, I) compounds in its matlockite-type structure

We present the results of the ab initio theoretical study of the optical properties for PbFX (X = Cl, Br, I) compounds in its matlockite-type structure using the full potential linearized augmented plane wave (FP-LAPW) method as implemented in the WIEN2K code. We employed generalized gradient approximation (GGA), which is based on exchange-correlation energy optimization to calculate the total energy. Also we have used the Engel-Vosko GGA formalism, which optimizes the corresponding potential for band structure calculations. Our calculations show that the valence band maximum (VBM) and conduction band minimum (CBM) are located at Z resulting in a direct energy gap. We present calculations of the frequency-dependent complex dielectric function ε( ω) and its zero-frequency limit ε₁ ( 0 ). We find that the values of ε₁ ( 0 ) increases with decreasing the energy gap. The reflectivity spectra and absorption coefficient has been calculated and compared with the available experimental data. The optical properties are analyzed and the origin of some of the peaks in the spectra is discussed in terms of the calculated electronic structure.     

Dielectric relaxation studies of alkanols solubilized by sodium dodecyl sulphate aqueous solutions

Considerable attention has been paid in recent years to the influence of alcohols on ionic micellar structures, alcohol co-surfactants most commonly employed in the preparation of microemulsions. Dielectric relaxation spectroscopy (DRS) is a versatile tool to monitor the dynamic process of such micellar systems. We report here the changes in the dielectric constant of the medium and the relaxation time of micellar solutions of sodium dodecyl sulphate (SDS) in water in the presence and absence of alkanols—hexan-1-ol, octan-l-ol, decan-l-ol and 1,2-ethanediol. The time domain dielectric data were obtained in the reflection mode in the frequency range of 10 MHz to 20 GHz using a HP54750A sampling oscilloscope and HP 54754A TDR plug-in-module. The sample is held at 303 K in a SMA cell with an effective pin length of 1.35 mm. We have determined the relaxation time (τ) using the Cole–Cole method. The relative viscosity ηr on the micellar solutions were also determined. The result shows that the dielectric constant increases linearly with SDS concentration in pure aqueous solutions up to 400 mM and decreases thereafter. The relaxation times are of the order of 15 ps to 25 ps and are far greater than that of Debye rotational relaxation of the monomer species. It is assigned to the dispersion step to water molecules surrounding to hydrophobic particles or the “bound water”. The addition of alcohols results in a linear increase in relaxation time in all the systems. As the concentration of SDS increases τ/ηr attains a near constant value showing that solubilization becomes more difficult at these concentrations. Our results show that the alcohol molecules are solubilized at the surface of the SDS micelle (i.e.) the micelle–water interface.     

Electrical resistivity of NaPb compound-forming liquid alloy using abinitio pseudopotentials

The study of electrical resistivity of compound-forming liquid alloy, NaPb, is presented as a function of concentration. Hard sphere diameters of Na and Pb are obtained through the interionic pair potentials evaluated using Troullier and Martinsab initio pseudopotential, which have been used to calculate the partial structure factors S(q). Considering the liquid alloy to be a ternary mixture, Ziman formula, modified for complex formation has been used for calculating resistivity of binary liquid alloys. Form factors are calculated usingab initio pseudopotentials. The results suggest that Ziman formalism, when used withab initio pseudopotentials, are quite successful in explaining the electrical resistivity data of compound-forming binary liquid alloys.     

The Fluorosolvatochromism of Brooker's Merocyanine in Pure and in Mixed Solvents

The fluorescence-based solvatochromism (fluorosolvatochromism) of 4-[(1-methyl-4(1H)-pyridinylidene)-ethylidene]-2,5-cyclohexadien-1-one (Brooker's merocyanine) was studied. The results revealed that the fluorescence emission band of the dye was dependent on the medium ( nm in water and nm in DMF). The fluorescence quantum yields (φ _f) were calculated for the dye in the solvents investigated. Low φ _f values ( < 10%) were obtained for the dye and in order to better comprehend the radiative and nonradiative decay processes of this dye, its fluorescence lifetime in methanol was measured and was found to be very short (230 ps). The results suggest that the dye in the excited state decays rapidly through nonradiative processes. The behavior of the probe in binary mixtures including a hydrogen-bond accepting solvent (acetonitrile, N,N-dimethylformamide, and dimethylsulfoxide) and a hydroxylic solvent (water, methanol, ethanol, propan-2-ol, and butan-1-ol) was also investigated. All data were successfully fitted to a model based on solvent exchange equilibria, which allowed the separation of the different contributions of the solvent species in the solvation shell of the dye. The data obtained for the mixed solvents were explained based on solute–solvent and solvent–solvent interactions.     

Microwave dielectric tangent losses in KDP and DKDP crystals

By adding cubic and quartic phonon anharmonic interactions in the pseudospin lattice coupled mode (PLCM) model for KDP-type crystals and using double-time temperature dependent Green's function method, expressions for soft mode frequency, dielectric constant and dielectric tangent loss are obtained. Using model parameters given by Ganguliet al [9] the dielectric losses are calculated for KDP and DKDP crystals. In the microwave frequency range an increase in frequency (1–35 GHz) is followed by an increase in dielectric tangent loss (1–35) at 98 K and (1–15) × 10⁻² at 333 K for KDP and DKDP crystals respectively. The dielectric tangent loss decreases from 0.052 to 0.042 for KDP crystals with increase in temperature from 130 to 170 K and for DKDP crystals it decreases from 0.0166 to 0.0074 with an increase in temperature from 230–343 K in their paraelectric phases at 10 GHz. This shows Curie-Weiss behavior of the dielectric tangent loss     

Optical,structural characterization and dielectric relaxation of [C2H5NH3]2ZnCl4 compound

ABSTRACT

The new organic-inorganic compound [C₂H₅NH₃]₂ZnCl₄ has been grown by the slow evaporation at room temperature. The zero-dimensional (0-D) structure for this compound was determined by the single X-ray diffraction. It crystallizes at room temperature in the non-centrosymmetric space group Pna2₁ and consists of ethylammonium cations [C₂H₅NH₃]⁺ and [ZnCl₄]^2? tetrahedra anions. That is interconnected by means of hydrogen bonding contacts N-H···Cl. The molecular geometry and vibrational frequencies of [ZnCl₄]^2? and [C₂H₅NH₃]⁺ in the ground state was calculated using density functional method (B3LYP) with 6–31G(d) and 6–311G (d,p) basis set. The optimized geometric bond lengths and bond angles, obtained by using B3LYP/6–311G (d,p), show the best agreement with the experimental data. The optical absorbance was measured in order to deduce the absorption coefficient α, optical band gap E_g. The optical band gap is determined by extrapolating the plotted graph of (αhυ)^1/2 vs. (hυ). The large value of indirect optical band gap energy indicates the insulating nature of this material. Moreover, the extinction coefficient, refractive index and the dielectric permittivity of [C₂H₅NH₃]₂ZnCl₄ compound were calculated and the results are discussed. The evolution of the dielectric loss as a function of frequency revealed a distribution of relaxation times, probably ascribed to the reorientational dynamics of alkyl chains in this compound, and then analyzed with the Cole–Cole formalism.     

Microwave dielectric response of binary mixture of N,N-dimethylformamide with propylene glycol using TDR method

Dielectric relaxation study of N,N-dimethylformamide (DMF) has been carried out with propylene glycol (PLG) at different temperatures. Time domain reflectometry (TDR) in reflection mode has been used to measure the reflection coefficient in frequency range of 10 MHz to 20 GHz. The dielectric parameters static dielectric permittivity (? ₀) and relaxation time (τ) have been obtained by Fourier transform and least squares fit methods. The experimental results show nonlinear variation in dielectric permittivity and relaxation time with volume fraction of PLG confirm the structural formation due to the intermolecular interaction between N,N-dimethylformamide and PLG. The variation in excess permittivity (ε ^E), excess inverse relaxation times (1/τ)^E, Kirkwood correlation factors (g ^eff, g ^f), activation enthalpy (ΔH) and entropy (ΔS) are also calculated to study the binary mixture interaction.     

Understanding the molecular interaction and relaxation findings in amphiphilics on solution state using TDR

The dielectric behavior of stearic acid in 1,4-dioxane medium at various temperature 303 K–288 K and frequency regime (10 MHz–30 GHz) determined from the complex dielectric permittivity spectra obtained by Time Domain Reflectometry(TDR). In this frequency range, the dielectric study gives the electrostatic interaction as well as orientational polarizability of complex mixtures of long chain molecules significantly. Dielectric parameters were calculated from the complex spectra of the binary mixture by non linear least square fit method. The excess permittivity (ε^E), correlation factors were calculated for the binary system. Thermal parameters(ΔH-enthalpy, ΔS-entropy and ΔG-Gibbs free energy) were calculated and the direction of reaction is determined. The FTIR spectrum of the binary system recorded and the assignments are discussed. The FTIR spectral assignments confirm the molecular interactions.     

An ab initio study of the structural,elastic, electronic and optical properties of the newly synthesized nitridoaluminate LiCaAlN2

The structural parameters, elastic constants, electronic structure and optical properties of the recently reported monoclinic quaternary nitridoaluminate LiCaAlN₂ are investigated in detail using the ab initio plane-wave pseudopotential method within the generalized gradient approximation. The calculated equilibrium structural parameters are in excellent agreement with the experimental data, which validate the reliability of the applied theoretical method. The chemical and structural stabilities of LiCaAlN₂ are confirmed by calculating the cohesion energy and enthalpy of formation. Chemical band stiffness is calculated to explain the pressure dependence of the lattice parameters. Through the band structure calculation, LiCaAlN₂ is predicted to be an indirect band gap of 2.725 eV. The charge-carrier effective masses are estimated from the band structure dispersions. The frequency-dependent dielectric function, absorption coefficient, refractive index, extinction coefficient, reflectivity coefficient and electron energy loss function spectra are calculated for polarized incident light in a wide energy range. Optical spectra exhibit a noticeable anisotropy. Single-crystal and polycrystalline elastic constants and related properties, including isotropic sound velocities and Debye temperatures, are numerically estimated. The calculated elastic constants and elastic compliances are used to analyse and visualize the elastic anisotropy of LiCaAlN₂. The calculated elastic constants demonstrate the mechanical stability and brittle behaviour of the considered material.     

High-resolution,near-infrared CW-CRDS,and ab initio investigations of N2O–HDO

We have investigated the N₂O–HDO molecular complex using ab initio calculations at the CCSD(T)-F12a/aug-cc-pVTZ level of theory and using cavity ring-down spectroscopy to probe an HDO/N₂O/Ar supersonic jet around 1.58 μm. A single a-type vibrational band was observed, 13 cm^?1 redshifted compared to the OH+OD excited band in HDO, and 173 vibration-rotation lines were assigned (T_rot ≈ 20 K). A weighted fit of existing microwave and present near infrared (NIR) data was achieved using a standard Watson's Hamiltonian (σ = 1.26), producing ground and excited states rotational constants. The comparison of the former with those calculated ab initio suggests a planar geometry in which the OD rather than the OH bond in water is almost parallel to NNO. The equilibrium geometry and dissociation energy (D_e = –11.7 kJ/mol) of the water–nitrous oxide complex were calculated. The calculations further demonstrate and allow characterising another minimum, 404 cm^?1 (ΔE₀) higher in energy. Harmonic vibrational frequencies and dissociation energies, D₀, were calculated for various conformers and isotopic forms of the complex, in both minima. The absence of N₂O–D₂O from dedicated NIR experiments is reported and discussed.     

Pressure effect on structural,electronic optical and thermodynamic properties of cubic AlxIn1-xP: a first-principles study

ABSTRACT

First-principles total energy calculations have been performed using the full potential linearised augmented plane wave (FP-LAPW) method as implemented in the WIEN2k code based on the density functional theory (DFT) to investigate the Al-doping effects on the structural, electronic and optical properties of Al_xIn_1-xP ternary alloys in the zinc-blende (ZB) phase. Different approximations of exchange-correlations energy were used such as the local density approximation (LDA), the generalised gradient approximation within parameterisation of Perdew–Burke–Ernzerhof (PBE-GGA), and the Wu-Cohen (WC-GGA). In addition, we have calculated the band structures with high accuracy using the Tran-Blaha modified Becke–Johnson (TB-mBJ) approach. The pressure dependence of the electronic and optical properties of binary AlP, InP compounds and their related ternary alloys Al_xIn_1-xP were also investigated under hydrostatic pressure for (P?=?0.0, 5.0,10.0, 15.0, 20.0, 25.0?GPa), where it is found that InP compound change from direct to indirect band gap for P?≥?9.16?GPa. Furthermore, we have calculated the thermodynamic properties of InP and AlP binary compounds as well as the Al_xIn_1-xP solid solutions, where the quasi-harmonic Debye model has been employed to predict the pressure and temperature dependent Gibbs free energy, heat capacity, Debye temperature and entropy.     

Decomposition pathways of C1C4 alcohols adsorbed on platinum (111)

The adsorption and decomposition of methanol, ethanol, propan-1-ol, propan-2-ol and butan-1-ol has been studied on clean, and oxygen pre-covered Pt(111) surfaces. Temperature Programmed Reaction Spectroscopy (TPRS), Surface Potential Measurements (ΔV), UPS and XPS were used to characterise the adsorbed layer as a function of temperature. Each alcohol adsorbed into two states, a monolayer phase and a multilayer phase which were distinguishable by TPRS and Spectroscopy measurements. The monolayer alcohol adsorption heats increased sequentially from methanol to n-butanol (11.5–15 kcal mole^?1). On the clean surface, less than 10% of the adsorbed monolayer dissociated, with 90% of the alcohol desorbing intact. Two competing dissociative pathways were observed: complete dissociation to adsorbed CO, H and C, and with propan-1-ol and butan-1-ol, scission of the CC bond nearest the CO group to form adsorbed CO, H and ethylidyne and propylidyne species respectively. The latter reaction probability was constant at 30% for n-propanol and n-butanol. In all cases the final desorption products were the parent alcohol, CO and H₂ with carbon remaining on the surface for the higher alcohols. Atomic oxygen removed hydrogen from the alcohols as water but did not change the final reaction products.