Effect of methylene spacer length on the molecular mobility and dipole moment of poly(azomethine esters) with azomethinearomatic groups in the ortho position

Relaxation of dipole polarization is studied and dipole moments are measured for poly(azomethine esters) with rigid azomethinearomatic fragments in the ortho position and methylene spacers of various lengths in the backbone chain. These polyesters in solution are shown to be characterized by four relaxation processes. The molecular mobility parameters (relaxation time and activation energies of three local processes) depend nonmonotonically on the length of the methylene spacer and on the evenness or oddness of the number of methylene units in the spacer in particular. For the fourth large-scale process, these activation parameters have high values and monotonically increase with the spacer length. The dipole moment of the polyester is shown to be higher when the number of methylene units in the spacer is odd. This may be due to specific conformational features of the ester part of the macromolecule.     

Electric dipole moments in polar solvents. II. Tetraisoamylammonium nitrate ion pairs in chlorobenzene. Effect of mutual polarization of the ions

The dielectric constant and conductivity of dilute solutions of tetraisoamylammonium nitrate in chlorobenzene are measured between –34.6° and 99.0°C to give association constants for the formation of ion pairs (K _A) and triple ions, and electric dipole moments. The quantityK _A as a function of temperature is reproduced by the Denison-Ramsey-Fuoss treatment for unolarized ion pairs [Eq. (2)] with a distance of closest approach of 4.90 Å. The dielectric data are reproduced by Onsager's equation with an inherent (gas-phase) dipole moment of the ion pairs of 14.2±0.3 D. Other methods of calculation lead to consistent dipole moments, confirming that the mutual polarization of the ions is important. The energetics of ionic association is considered on the basis that the ion pair may be treated as a polarizable dipole in a spherical cavity.     

Effects of orientation on the mechanical and dielectric relaxation behavior of cycloaliphatic polyester networks

The mechanical and dielectric relaxation behavior of strained and unstrained networks, prepared from hydroxyl-terminated poly(diethylene glycol-trans-1,4-cyclohexane dicarboxylate) (PDGC), is studied over a wide interval of frequencies and temperatures. The mechanical relaxation spectrum exhibits a glass-rubber absorption, designated β, located in the vicinity of 0°C at 0.1 Hz, followed by a β relaxation which appears to be the result of two overlapping peaks centered at ?80°C (β₁) and ?110°C(β₂). These two peaks coalesce into a single peak in the case of strained networks. The dielectric relaxation spectrum also exhibits an α absorption followed by a subglass β relaxation whose width decreases as the elongation ratio λ increases. The activation energy associated with the mechanical β₁ appears to increase as λ increases. However, the activation energy of the dielectric β process does not show a clear dependence on the elongation ratio. The analysis of the conformational characteristics of PDGC chains indicates that rotational transitions through the C_cy? C* bonds of the acid residue would give rise to high dielectric activity. Conformational changes about the CH₂? CH₂ bonds of the glycol residue would produce significant mechanical activity but, comparatively, low dielectric activity. The glass-rubber absorption is slightly displaced toward the high-temperature side as the elongation ration increases, suggesting that the entropic effects overcome the volume effects. The glass-rubber transition is interpreted in terms of the free volume theory.     

Solution Properties of NaHSO4 and Na2SO4: A New Sight from the Water–Ion and Water–Dipole Cooperative Interactions Using Dielectric Relaxation Spectroscopy

The aqueous NaHSO₄ and Na₂SO₄ solutions at concentrations of 0.1–1.0 mol/l in a limited frequency range 0.2–20 GHz are studied by dielectric relaxation spectroscopy with a newly developed fractal concept spectral function. The fractal analysis with α(lnτ) diagrams from dielectric relaxation spectroscopy as functions proposed a new strategy to shed light on the dual nature of ion–water and dipole–water cooperative interactions. A distinct cooperative interaction of ion–water and dipole–water is observed and water molecules perturbed by ions contributing to dielectric constant beyond the first hydration shell is obtained.     

Electrorheology of aniline oligomers

Aniline oligomers were prepared by the oxidation of aniline with p-benzoquinone in aqueous solutions of methanesulfonic acid (MSA) of various concentrations. Their molecular structures were assessed by Fourier transform infrared spectroscopy. The electrorheological (ER) behavior of their silicone oil suspensions under applied electric field has been investigated. Shear stress at a low shear rate, τ _0.9, was used as a criterion of the rigidity of internal structures created by the application of an electric field. It was established from the fitting of the dielectric spectra of the suspensions with the Havriliak–Negami model that dielectric relaxation strength, as a degree of polarization induced by an external field contributing to the enhanced ER effect, increases and relaxation time, i.e., the response of the particle to the application of the field, decreases when a higher molar concentration of MSA is used. The best values were observed for suspensions of the sample prepared in the presence of 0.5 M of MSA. This suspension creates stiff internal structures under an applied electric field strength of 2 kV mm^?1 with τ _0.9 of nearly 50 Pa, which is even slightly of higher value than that obtained for standard polyaniline base ER suspension measured at the same conditions. The concentration of the MSA used in the preparation of oligomers seems to be a crucial factor influencing the conductivity, dielectric properties and, consequently, rheological behavior, and finally ER activity of their suspensions.     

Electrostatic and relaxation effects in ionization of molecular dimers and intermolecular complexes

The shifts in ionization energies which occur when a molecule is incorporated as an asymmetric dimer or in an intermolecular complex are analyzed theoretically. MO ? SCF calculations with 4–31G basis sets were performed on closed- and open-shell states of (HF)₂, H₂O·HF, and their valence–hole ions, as well as on the heterodimers incorporating the higher homologues CH₃F, CH₃OH, and (CH₃)₂O. The analysis concerns the influence of electrostatic, polarization, and charge transfer effects associated with complexation on the initial molecular state of each monomer system, as well as monomer–dimer differences in the electronic relaxation mechanism considered as a final state effect in the ionization process. The calculated ionization energy shifts which agree well with the experimental data available for (CH₃)₂O·HF, show that the shifts are dominated by electrostatic effects, but some effects arising from differences in molecular size and electric polarizability of the monomers can be discerned.     

Dielectric study of dipolar association in dilute solutions of nitrobenzene in benzene

The correlation factors R_p and R_s are determined for the dielectric polarization and the non-linear dielectric effect in dilute solutions of nitrobenzene in benzene. Assuming dipole association of the nitrobenzene molecules to be restricted to dimerization, we determined the concentration x₂ of dimers, their dipole moment μ_dim, and the equilibrium constant K_x and Gibbs energy ΔG of the dimerization process.     

THE EFFECT OF ACCEPTOR GROUP VARIATION ON THE SOLVATOCHROMISM OF DONOR-ACCEPTOR FLUOROPHORES

Abstract The absorption and emission characteristics of five hydroxytetrahydrochrysenes substituted with acceptor groups (nitro, cyano, methylketone, 1° amide and methyl ester) (THC-NO₂, THC-CN, THC-COCH₃, THC-CONH₂ and THC-CO₂CH₃, respectively) were investigated in an extensive set of solvents. The order of absorption and fluorescence bathochromicity are: THC-NO₂ > THC-COCH₃ > THC-CN ≥ THC-CO₂CH₃ > THC-CONH₂ and THC-NO₂ >> THC-COCH₃ > THC-CO₂CH₃ > THC-CN > THC-CONH₂, respectively. The emission spectra of these compounds are sensitive to the solvent polarity (E_T[30] scale) in the order: THC-NO₂ > THC-COCH₃ > THC-CO₂CH₃ > THC-CONH₂ > THC-CN. The response of the emission maxima of these compounds to the solvent polarity and hydrogen-bond donor/acceptor properties (π*/α/β and acity/basity scales) was also determined. The emission energies of THC-NO₂ were most sensitive to π*, β, acity, and basity of the solvent; those of the amide were least sensitive to the solvent π*, β, and basity. The ground- and excited-state dipole moments were determined by semiempirical molecular orbital calculations and the absorption/fluorescence solvent-shift method, respectively. THC-NO₂ had the largest ground- and excitedstate moments. The ester and amide had the smallest ground- and excited-state moments, respectively. In general, unsatisfactory results were obtained for correlations of the emission and absorption energies, fluorescence solvatochromism and the ground- and excited-state dipole moments with the Hammett substituent constants of the five acceptor groups. Acceptable correlations were obtained for the absorption and emission energies and the fluorescence solvatochromism with the substituent constants if the cyano compound was excluded.     

Fluorescence depolarization in polymers: The microviscosity of bulk polybutadiene and of solutions in cyclohexane

The reorientational relaxation of 9-cyananthracene fluorescent label molecules has been measured in bulk polybutadiene and solutions with cyclohexane by a fluorescent depolarization technique. The procedure adopted consists in the incorporation of an Arrhenius temperature dependence of the orientational relaxation time in the Perrin equation, thus obviating the necessity of an independent determination of the intrinsic polarization ratio P₀ and enabling one to obtain the preexponential factors and the activation energies of the reorientational relaxation times. The most noteworthy result in our view is the validity of the Arrhenius equation for the effective microviscosity as opposed to the validity of the Fulcher–Vogel–Tamann equation with a glass point of T₀ = 136 K for the shear viscosity of a polymer solution (90%).     

Mechanisms of molecular polarization of bithiophenesilane dendrimers in solutions

A number of consecutive generations of bithiophenesilane dendrimers and their precursors are studied by the methods of the equilibrium electro-optical Kerr effect, dielectric polarization, and absorption spectroscopy in dilute toluene solutions. It is shown that the molecules of hybrid dendrimers containing bithiophene fragments covalently linked via silicon atoms are not kinetically rigid and feature the small-scale mechanism of interaction with external electric fields. A tris(bithiophene)methylsilane fragment is found to be the subunit responsible for the electro-optical and optical spectral properties of the above hybrid dendrimers. It is revealed that the polarization of bithiophensilane dendrimers predominantly shows the deformation pattern.     

Simulation of volume polarization for the influence of solvation on chemical shielding

The effect of bulk dielectric solvation on chemical shielding at nitrogen in CH₃CN is studied with reaction field theory. A previous work has demonstrated the strong influence on this property from volume polarization, which describes that part of the reaction field arising from solute charge density penetrating outside its cavity. The essentially exact treatment of volume polarization used in that work is computationally demanding, and a more facile method for simulation of the volume polarization has recently been proposed. It is found in the present work that this simulation of the volume polarization yields results in excellent agreement with the essentially exact treatment of the strong volume polarization effects on nitrogen shielding in CH₃CN.Contribution to the Jacopo Tomasi Honorary Issue     

Dielectric polarization and non-linear dielectric effects in pivalonitrile solutions

Dielectric polarization and non-linear dielectric studies of solutions of pivalonitrile (CH₃)₃CN in carbon tetrachloride, cylohexane and n-hexane are presented. The contributions of Langevin orientation, dipolar coupling and pretransitional fluctuations have been separated from the observed dielectric non-linear effect.     

Preparation and electrorheological properties of triethanolamine-modified TiO2

The high molecular dielectric dipole moment of doping material is promising to improve the electrorholegical (ER) effect. It is found that triethanolamine (the molecular dipole moment of triethanolamine is 3.48)-modified TiO₂ has good ER properties. Under 5 kV/mm external electric field, the yield stress is 32.6 kPa, which is about 50 times higher than that of pure TiO₂ and the leaking electric current density is lower than 16 μA/cm². The sedimentation rate is about 98% in 20 days.     

Mode-specific pressure effects on the relaxation of an excited nitromethane molecule in an argon bath

The vibrational and rotational mode-specific relaxations of CH₃NO₂ with 50 kcal/mol of initial internal energy in an argon bath is computed at 300 K at pressures of 10-400 atm. This work uses archived information from our previously published [J. Chem. Phys. 142, 014303 (2015)] molecular dynamics simulations and employs our previous published [J. Chem. Phys. 151, 034303 (2019)] method for projecting time-dependent Cartesian velocities onto normal mode eigenvectors. The computed relaxations cover three types of energies: vibrational, rotational, and Coriolis. In general, rotational and Coriolis relaxations in all modes are initially fast followed by an orders of magnitude slower relaxation. For all modes, that slower relaxation rate is approximately comparable to the vibrational relaxation rate. For all three types of energies, there are small-scale mode-to-mode variations. Of particular prominence is the exceptionally fast relaxation shared in common by the external rotation about the C N axis, the internal hindered rotation of the CH₃ group relative to the NO₂ group, and the symmetric stretch of the CH₃ group.     

Conformational properties of polar polymers. I. Poly(vinyl chloride)

A recently developed method for including polar bonds in conformational energy calculations is applied to poly(vinyl chloride). Inductive effects on dipole moments and the effects of intervening atoms on electrostatic interaction energies are represented by polarizability centers in conjunction with bond centered dipoles. Solvation energies are estimated by means of a continuum dipole–quadrupole electrostatic model. Calculated energies of a number of conformations of meso and racemic 2,4-dichloropentane and the iso, syndio, and hetero forms of 2,4,6-trichloroheptane give satisfactory representations of isomer and conformer populations. Electrostatic effects are found to be quite important. However they appear to be effectively of sufficiently short range that the calculated conformer energies are found to be fit well by a linear combination of interaction parameters (consisting of gauche, skew chlorine, four-bond CH₂…CH₂, CH₂…Cl, and Cl…Cl interactions) conventional to vinyl polymers and a special four-bond interaction that arises when the bond sequence Cl? CH? CH²? CH? Cl is (nearly) coplanar. These interaction parameters when assembled into statistical weight matrices lead to calculated values of both the characteristic ratio and the dipole moment ratio in satisfactory agreement with experiment. Least energy paths for transitions between the most stable conformations are also calculated.     

Hydrogen-Bond Structure and Low-Frequency Dynamics of Electrolyte Solutions: Hydration Numbers from ab Initio Water Reorientation Dynamics and Dielectric Relaxation Spectroscopy

We present an atomistic simulation scheme for the determination of the hydration number (h) of aqueous electrolyte solutions based on the calculation of the water dipole reorientation dynamics. In this methodology, the time evolution of an aqueous electrolyte solution generated from ab initio molecular dynamics simulations is used to compute the reorientation time of different water subpopulations. The value of h is determined by considering whether the reorientation time of the water subpopulations is retarded with respect to bulk-like behavior. The application of this computational protocol to magnesium chloride (MgCl₂) solutions at different concentrations (0.6–2.8 mol kg⁻¹) gives h values in excellent agreement with experimental hydration numbers obtained using GHz-to-THz dielectric relaxation spectroscopy. This methodology is attractive because it is based on a well-defined criterion for the definition of hydration number and provides a link with the molecular-level processes responsible for affecting bulk solution behavior. Analysis of the ab initio molecular dynamics trajectories using radial distribution functions, hydrogen bonding statistics, vibrational density of states, water-water hydrogen bonding lifetimes, and water dipole reorientation reveals that MgCl₂ has a considerable influence on the hydrogen bond network compared with bulk water. These effects have been assigned to the specific strong Mg-water interaction rather than the Cl-water interaction.     

Radiowave dielectric investigation of water confined in channels of carbon nanotubes

Structure and dynamics of water confined in channels of diameter of few nanometer in size strongly differ from the ones of water in the bulk phase. Here, we present radiowave dielectric relaxation measurements on water-filled single-walled carbon nanotubes, with the aim of highlighting some aspects on the molecular electric dipole organization of water responding to high spatial confinement in a hydrophobic environment. The observed dielectric spectra, resulting into two contiguous relaxation processes, allow us to separate the confined water in the interior of the nanotubes from external water, providing support for the existence in the confinement region of water domains held together by hydrogen bonds. Our results, based on the deconvolution of the dielectric spectra due to the presence of a bulk and a confined water phase, furnish a significantly higher Kirkwood correlation factor, larger than the one of water in bulk phase, indicating a strong correlation between water molecules inside nanotubes, not seen in bulk water.     

Coherent excitation of H(n=2) in H+, H - He collisions

The coherent excitation of H(n=2) in H⁺, H - He collisions was investigated at incident energies of 5–25 keV. From a polarization analysis of the emitted Lyman-α radiation as a function of an external electric field, the partial cross sections for excitation to the H(2s) and the H(2p _m) magnetic substates and the real part of thes ?p ₀-coherence were extracted. For H⁺-He collisions, the measured partial cross sections are in fair agreement with previous two-electron calculations by Kimura and Lin; the agreement with one-electron calculations of Jain et al. is, particularly at the lower incident energies, less satisfactory. For both collision systems, an energy-dependent forward-backward asymmetry corresponding to a shift of the center-of-charge relative to the center-of-mass (dipole moment) was observed. In H⁺ - He collisions, the measured dipole moment was positive; it thus corresponds to an electron trailing behind the proton. The same analysis applied to the H - He system showed the electron riding in front of the proton.     

Analysis of initial energies of fragments produced by 65-keV proton-molecule collisions using a time-of-flight mass spectrometer

A method is described to evaluate initial-energy distributions of fragments produced by proton-molecule collisions. The fragments are analysed by means of a time-of-flight mass spectrometer and their initial energies are evaluated from their time-of-flight spectrum. These energies are presented for various fragments of H₂, N₂, O₂, CO₂, CH₃Cl, CH₃Br, CH₃I, C₂H₆ and C₃H₈ produced with 65-keV protons. The results indicate the generation of several energetic fragments of the halomethanes, ethane and propane via dissociation of a doubly charged molecule followed by evaporation of one or more hydrogen atoms.