Dielectric alignment of a non-polar molecule substituting a polar molecule in a lattice of molecular dipoles

The dielectric alignment of a dilute non-polar component in a polar solvent may be determined by NMR spectroscopy. In this paper a series expansion of the alignment up to second order terms in the dipolar interaction is presented for a non-polar molecule replacing a single polar molecule in a rigid lattice of molecular dipoles. Assuming isotropic polarizabilities for all molecules Van Vleck earlier applied the lattice model in a theory of the dielectric constant of a dilute solution.In the present calculation the polarizabilities of the non-polar molecule and the dipoles are assumed to be anisotropic and isotropic, respectively. The anisotropy of the non-polar molecule is relevant, since the value of the alignment is zero for the isotropic case. Different results are obtained for cubic lattices and for a lattice points are uniformly distributed.In absence of a rigid dipole moment of the solvent molecules the latter formula may be compared with that implicity deduced by Buckingham for the Kerr effect. In the limit of strong dipoles the orientation imposed by the rigid dipole moments appears to be the major contribution to the alignment of the non-polar molecule.     

Anchoring transitions with polar and non-polar nematic liquid crystals on incompletely oxidized silane substrates

The active oxygen gas arising from a plasma reactor is used to realize progressive chemical modifications onto silane coatings that could be particularly interesting as alignment layers for liquid crystal display applications. Depending on the oxygen density grafted onto the substrate, these alignment layers provide different zenithal anchoring angles, or pretilt angles, with anchoring transitions, for polar and non-polar nematic liquid crystals as 5CB and MBBA, respectively. The anchoring transitions are found to be smoother with the polar nematics. Such a behavior is discussed in terms of the differential wetting model by adding a cosine term to the interaction energy between the nematic and the substrate. A local justification is proposed for this symmetry breaking term. Received: 18 May 1998     

向列相液晶沿面到垂面排列转变的分子场理论

以摩擦基板间的液晶薄层为研究对象,用分子场理论研究了向列相液晶分子排列转变行为.分子质心固定在简单立方晶格的格点上.液晶由极性分子构成,与基板相接触的一层分子同时受到色散和极性两类表面作用.通过自洽的数值计算,获得3种相图,清楚地展示了摩擦基板间向列相出现的从高温沿面到低温垂面排列的转变;获得实现这类转变所需要的两类表面作用的参数范围.结果表明:基板的摩擦会改变基板表面色散作用,但不会影响基板表面极性作用;表面极性相互作用能引起基板间向列相液晶发生沿面到垂面排列转变.     

Double-exchange ferromagnetism in the partially-filled one-dimensional Kondo lattice model

We investigate the incompletely saturated ferromagnetic phase which occurs at strong-coupling in the partially-filled one-dimensional (1D) Kondo lattice model. The double-exchange interaction responsible for the ferromagnetic ordering is absent in dilute Kondo systems, and is a missing element in nearly all theoretical treatments of the model. We discuss how: 1) double-exchange arises in the system, even though the Kondo coupling is antiferromagnetic, and show that at strong-coupling it favors an alignment of the spins of unpaired localized moments; and 2) how this determines the ground-state phase diagram, and properties of the localized moments.     

Alignment of non-polar molecules—electric field effects in the 2H N.M.R. spectrum of perdeuterobenzene in solutions with nitrobenzene

Electric field experiments on the ²H N.M.R. spectrum of perdeuterobenzene, dissolved in nitrobenzene, are reported. The alignment of the polar molecules, induced by a strong electric field, is transferred to the non-polar ones and as a result their N.M.R. spectrum is modified.

Local field models, e.g. those of Lorentz and Onsager, treat the environment of a molecule as a continuum and are unable to explain the alignment of the non-polar molecules. Intermolecular interactions are essential. In an expression for the alignment these interactions are described in terms of correlation functions for the mixture.

N.M.R. and Kerr data of nitrobenzene-benzene solutions have been compared. The Kerr constant of a binary mixture is shown to depend on the alignments of both the polar and non-polar component. N.M.R. electric field experiments may be useful to separate these two contributions.     

Potential of mean force for ion pairs in non-aqueous solvents. Comparison of polarizable and non-polarizable MD simulations

Potentials of mean force (PMF) are calculated for two model ion pairs in two non-aqueous solvents. Standard non-polarizable molecular dynamics simulation (NPMD) and approximate polarizable simulation (PMD) are implemented and compared as tools for monitoring PMF profiles. For the polar solvent (dimethylsulfoxide, DMSO) the PMF generated in terms of the NPMD reproduces fairly well the refined PMD–PMF profile. For the non-polar solvent (benzene) the conventional NPMD computation proves to be deficient. The validity of the correction found in terms of the approximate PMD approach is verified by its comparison with the result of the explicit PMD computation in benzene. The shapes of the PMF profiles in DMSO and in benzene are quite different. In DMSO, owing to dielectric screening, the PMF presents a flat plot with a shallow minimum positioned in the vicinity of the van der Waals contact of the ion pair. For the benzene case, the observed minimum proves to be unexpectedly deep, which manifests the formation of a tightly-binded contact ion pair. This remarkable effect arises owing to the strong electrostatic interaction that is incompletely screened by a non-polar medium. The PMFs for the binary benzene/DMSO mixtures display intermediate behaviour depending on the DMSO content.     

Effect of dipole-dipole interaction in a solvent on the electronic spectra of three-component solutions

Electronic spectra of three-component solutions are calculated on the basis of a model, which makes it possible to incorporate the interaction between the molecules of a polar solvent, including the case of dielectric saturation. It is shown that the use of the theory of three-component solutions, which disregards the interaction between the molecules of a polar solvent, can lead to an overestimation of the efficiency with which an activator interacts with the molecules of a polar solvent. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 1, pp. 38–41, January–February, 2000.     

Dependence of vibrational density of states and Raman spectra on size in non-polar and polar nano-crystalline semiconductors

The vibrational density of states (VDOS) of Si, diamond, SiC, and InSb clusters has been calculated using the cluster model for various cluster sizes. The results show that the peak frequency of optical-like bands of VDOSs of non-polar nano-crystalline (NC) semiconductors varies with size, but that of polar NC semiconductors does not vary with size. We attribute the origin of this different behavior of non-polar and polar NC semiconductors to different interactions in the optical-like modes of them. That is, the deformation potentials for the non-polar NC semiconductors and electrostatic potentials for the polar NC semiconductors. According to the amorphous crystal (aC) model, Raman spectra are directly related to VDOS. In this Letter, it is verified that the aC model can be applied to NC semiconductors. Calculated VDOS are compared with observed Raman spectra of corresponding samples, which show agreement.     

Solvent effects on radiationless transitions

A quantum mechanical theory of the solvent effect on radiationless transitions is developed within the framework of a dynamic coupling model. This model allows us to describe the solvent effect on any mechanism of intramolecular radiationless transition, in polar as well as non-polar solvents.     

The Temperature Dependence of the Effective Mass of a Two-Dimensional Polaron

The properties of a two-dimensional polaron in the polar crystal are discussed by means of a model which takes account of the atomicity of the lattice. The lattice vibration and the interaction between the electron and the lattice displacement are treated by second quantization-method. The self-trapped energy and the effective mass of the two-dimensional polaron are derived.     

Alignment of polarizable dipoles on a lattice

The alignment average of polar molecules may be derived from their NMR spectrum, when a strong electric field is applied to the liquid. The Kerr effect can likewise be related to the alignment.In this paper the alignment has been calculated for a rigid-lattice model, previously developed by Van Vleck in the theory of dielectric polarization and extended by others. A series expansion of the alignment for a system of isotropically polarizable dipoles is presented up to second-order terms in the dipolar interaction. The result for a continuum has been compared with those calculated on the basis of the Lorentz and Onsager model of the liquid.An explicit expression for the total electrostatic energy of a binary mixture of polar and non- polar molecules with a symmetric polarizability tensor has also been calculated; it has been obtained from a generalization of a formalism, developed by Mandel and Mazur for the pure polar liquid.     

A comparative study of non-polar solvents effect on dielectric relaxation and dipole moment of binary mixtures of mono alkyl ethers of ethylene glycol and of diethylene glycol with ethyl alcohol

Dielectric relaxation and dipole moment of binary mixtures of homologous series of mono alkyl ethers of ethylene glycol and of diethylene glycol, i.e., mono methyl, mono ethyl and mono butyl ethers of ethylene glycol (ROCH₂CH₂OH) and mono methyl, mono ethyl and mono butyl ethers of diethylene glycol (ROCH₂CH₂OCH₂CH₂OH) with ethyl alcohol (C₂H₅OH) of different concentrations were studied in dilute solutions of benzene, dioxane and carbon tetrachloride at 35 °C. Permittivity (ε′) and loss (ε″) at 10.1 GHz, static dielectric constant ε_o at 1 MHz and high frequency limiting dielectric constant ε_∞ = n_D² at optical frequency of these molecules and their binary mixtures at different concentration were measured in dilute solutions of non-polar solvents. The average relaxation time τ_o, relaxation times corresponding to overall molecular reorientation τ₁ and group rotations τ₂ were determined using Higasi's single frequency measurement equations for dilute solutions. The evaluated values of relaxation times and free energy of activation ΔF were used to explore the solvent effect on molecular dynamics of these polar binary systems in non-polar solvents. The excess inverse relaxation time and excess free energy of activation were determined to confirm the existence of hydrogen-bonded heterogeneous cooperative domains of the ethers and alcohol molecules at different concentration their binary mixtures in non-polar solvents. The dipole moment of the binary mixtures was evaluated using Higasi's and Guggenheim's equation for dilute solutions. The evaluated values of dipole moments and computed dipole moment values using a simple mixing equation of the polar molecules binary mixture were used to explore the effect of non-polar solvent environment on heterogeneous molecular interactions between ethers and alcohol molecules. The effect of number of carbon atoms in the molecular structure of these homologous series molecules was also considered for the interpretation of various evaluated dielectric parameters.     

Optimization in Solvent Selection for Chlorin e6 in Photodynamic Therapy

The photophysical properties of chlorin e6 (Ce6) in twelve different protic, aprotic and non-polar solvents were investigated using ultraviolet–visible and fluorescence spectroscopic methods. Solvatochromic effects were determined by the changes in quantum yield, Stokes shift, fluorescence half-life and excited state dipole moments of Ce6 in the different solvents. The absorption shifts observed in different solvents were further analyzed using the Kamlet-Abboud-Taft model and the nature of solute-solvent interactions between Ce6 and different protic and aprotic solvents was elucidated. The quantum yields were found highest in protic solvents (except water), followed by aprotic and non-polar solvents. Solvent polarity parameters showed a linear increasing trend with Stokes shift and fluorescence half-life, which indicated the presence of Ce6-solvent interaction. Using the Kamlet-Abboud-Taft model, a direct correlation between the solvent polarity parameters and absorption shift was observed, which substantiated the existence of Ce6-solvent interaction by hydrogen bond formation. The excited state dipole moments in specific protic and aprotic solvents were found to be higher than the ground state dipole moments, implying a more polar nature of Ce6 during excited state transition.     

The effect of crystal equilibrium condition on the lattice dynamical model parameters of a body centred cubic metal

Using barium, for which results that compare favourably with experiment have been obtained, the effect on the lattice dynamical model parameters of a body centred cubic metal of explicitly imposing the crystal equilibrium condition on various ion-ion coupling schemes when used with the modified electron-ion interaction scheme of Bhatia has been studied. When the equilibrium condition is not used, the calculated model parameters lose their physical significance with the result that at equilibrium, the sum of the ionic and electronic pressures is not zero. This inconsistency is removed when the equilibrium condition is explicitly imposed on the models. It is not meaningful to compare the two results with and without the equilibrium condition imposed, not only because the imposition of the equilibrium condition reduces the number of independent parameters of the models by one, but also because the results apply to different states of the crystal. Also the comparison of calculated model parameters and measured quantities such as phonon frequencies make sense only when both are determined for the same state of the crystal. This condition is satisfied only when the equilibrium condition, which has unfortunately been ignored in most lattice dynamical studies, is explicitly imposed on lattice dynamical models.     

Effect of positional substitution of amino group on excited state dipole moments of quinoline

The effect of positional substitution of amino group on the ground and excited state dipole moments of quinoline ring has been investigated using solvatochromic shift methods. The excited state dipole moments of 5aminoquinoline (5AQ) and 3aminoquinoline (3AQ) have been estimated from the spectral data in different non-polar, polar aprotic and polar protic solvents using Bakhshiev and Kawski-Chamma-Viallet equations. It has been observed that both grounds as well as excited state dipole moments for 5AQ are higher than those for 3AQ by approximately a factor of two. Higher values of the excited state dipole moments for both 3AQ and 5AQ as compared to corresponding ground state values have been attributed to intramolecular charge transfer processes. The role of specific solute-solvent interaction on excited state dipole moment in addition to the general solvent effects has been discussed.     

3-d Model for strain ordering in steel: I Static effects

We present a spring-defect model in 3-dimensions to describe the connection between elastic distortion and interstitial carbon ordering associated with phase transition from a body centred cubic (BCC) to body centered tetragonal (BCT) structure in BCC metals such as α-iron. The presence or the absence of the carbon is modelled in terms of a pseudo spinŝ=+1or -l.An Ising interaction between carbon atoms is recovered after eliminating the lattice degrees of freedom, which is longranged. The coupling between the spin and lattice degrees of freedom allows for a systematic study of ferroelasticity and the variation of the lattice parameter with carbon concentration. The mean field results for the paraelastic to ferroelastic transition, lattice parameter and static compliance are presented. The significant feature of this calculation is not only a derivation of the defect-defect interaction, but also an explicit calculation of the strain dipole tensor associated with each defect, from a microscopic model.     

Effect of dielectric properties of solvents on the quality factor for a beyond 900 MHz cryogenic probe model

A previous report by Kelly et al. [J. Am. Chem. Soc. 124 (2002) 12013] indicated that the ionic conductivity of aqueous solution produces a significant contribution to the sensitivity loss in high-resolution NMR equipped with a cryogenically cooled probe. The loss in a sample solution contains two contributions: one from the ionic conductivity and the other from the dielectric loss; the latter is especially important at high frequencies such as above 900 MHz. Here, we investigated the effect of the dielectric conductivity on the quality factor of a 930 MHz cryogenic probe model; in particular, it deals with the ionic aqueous solutions and organic solvents commonly used for NMR in biological research and the chemistry of natural compounds. The sample quality factor, Qs, at first increases with the real part of the relative dielectric permittivity epsilon' and then saturates. In the case of polar organic solvents, the transverse electric field on the sample decreases with epsilon', resulting in an increase of Qs. In the case of non-polar organic solvents, the dielectric conductivity is so small that the gradient of the increase is steep, resulting in much larger Qs though the epsilon' is small. The effect of the transverse electric field is negligible if the epsilon' becomes large, thus the loss for ionic aqueous solution is mainly governed by a loop current induced in the sample solution. As the induced electromotive force is independent of the epsilon', the Qs is saturated at high values of epsilon'. Based on the Qs obtained with the cryogenic probe model, the sensitivity for the cryogenic probe is expected to be as follows: the loss in sensitivity by loading water is more than 66%, i.e., the effect of the dielectric conductivity of water is remarkable at high frequencies; polar organic solvent suffers much larger losses, which is due to the enhancement of the effective sample resistance by the effect of epsilon'; a non-polar organic solvent is nearly free of the sensitivity loss as the dielectric conductivity is negligible; the reverse micelle behaves similarly.     

Electron-TO-phonon interaction in polar crystals

In the present work, the interaction between electrons and long-wavelength transverse optical (TO) vibrations in a polar insulator is considered. The crystal model employed for the theoretical analysis includes classical potentials and electronic polarizabilities. A significant enhancement of the strength of the electron-TO-phonon interaction in ferroelectrics has been found. A microscopic justification of this effect is given. A bridge that relates the interaction of electrons with the polar long-wavelength TO modes of lattice vibrations to the long-range dipole-dipole interaction is established. As an application of our analysis, a novel method for quantitative predictions of the electron-TO-phonon interaction constants in polar crystals via the data of experimental studies is suggested.