Do bacteria have an electric permanent dipole moment?

In the scientific literature in the last 40 years, some data for the permanent dipole moment and the electric polarizability of Escherichia coli can be found [S.P. Stoylov, Colloid Electro-Optics - Theory, Techniques and Application, Academic Press, London, 1991]. In this paper the data based mainly on electro-optic investigation is considered as much as some dipolophoretic (most often called dielectrophoretic) studies. Serious grounds are found to doubt the conclusions made for the electric dipole moments of bacteria by one of the authors of this paper (SPS) and by some other researchers. This concerns both the permanent dipole moment and the electric charge dependent polarizabilities of E. coli. Here, along with the discussion of the old experimental data, new experimental data are shown for a strain of E. coli HB101. The conclusions from the analysis of the old and the new experimental data is that they do not provide correct evidence for the presence of a permanent dipole moment. It seems that all statements for the existence of electric permanent dipole moment in bacteria [S.P. Stoylov, Colloid Electro-Optics - Theory, Techniques and Application, Academic Press, London, 1991; S.P. Stoylov, S. Sokerov, I. Petkanchin, N. Ibroshev, Dokl. AN URSS 180 (1968) 1165; N.A. Tolstoy, A.A. Spartakov, A.A. Trusov, S.A. Schelkunova, Biofizika 11 (1966) 453; V. Morris, B. Jennings, J. Chem. Soc. Faraday Trans. II 71 (1975) 1948; V. Morris, B. Jennings, J. Colloid Interface Sci. 55 (1978) 313; S.P. Stoylov, V.N. Shilov, S.S. Dukhin, S. Sokerov, I. Petkanchin, in: S.S. Dukhin (Ed.), Electro-optics of Colloids, Naukova Dumka, Kiev, 1977 (in Russian).] based on electro-optic studies are result of incorrect interpretation. Therefore, they should be further ignored.     

Unified Treatment for Arbitrary-rank Cartesian Electric and Magnetic Multipole Moment Operators

In this study, the theory of cartesian electric and magnetic multipole moments is extended in a unified way. The general analytical expressions for distinct components of arbitrary rank cartesian electric and magnetic multipole moment operators are derived as linear combination of corresponding spherical operators, which can be used as interconversion between cartesian and spherical electric and magnetic multipole moment tensors. The transformation properties, such as translation and rotation of cartesian electric and magnetic multipole moments are given in a very simple general form. The relationship between distinct and linearly independent components of cartesian multipole moment tensors in system of linear symmetry is also presented. The formulae obtained in this paper can be utilized to calculate the interaction energies between charge distributions.     

Electric properties of molecules confined by the spherical harmonic potential

The harmonic oscillator potential is very often used in quantum chemical studies of electric properties to model the effect of spatial confinement. In the vast majority of works, the harmonic potential of cylindrical symmetry was applied. Thus far, its spherical counterpart was used mainly to describe properties of spatially restricted atomic systems. Therefore, our main goal was to study the molecular electric properties in the presence of the spherically symmetric harmonic oscillator potential and to characterize the impact of the relative position of the considered molecules and spherical confinement on these properties. Moreover, we analyzed how the topology of confining environment affects the dipole moment and (hyper)polarizability, by comparing the results obtained in the spherical and cylindrical harmonic potential. Based on the conducted research, it was found that the position of the molecules relative to the spherical confinement strongly influences their electric properties. The observed trends of changes in the electric properties, caused by increasing the confinement strength, vary significantly. Moreover, it was shown that in the vast majority of cases, significant differences in the values of electric properties, obtained in the cylindrical and spherical confinement of a given strength, occur.     

Polarized basis sets for accurate calculations of static and dynamic electric properties of molecules

We report on the development and testing of large polarized basis sets (LPolX, where X is the element symbol) for accurate calculations of linear and nonlinear electric properties of molecules. The method used to generate LPolX sets is based on our studies of the analytic dependence of Gaussian functions on external time‐independent and time‐dependent electric fields. At variance with the earlier investigations of small, highly compact (ZPolX) basis sets for moderately accurate calculations of electric properties of large molecules, the present goal is to obtain basis sets that are nearly saturated with respect to the selected class of electric properties and can be used for accurate studies of interaction‐induced properties. This saturation makes the LPolX sets also useful in calculations of optical properties for chiral molecules. In this article, the LPolX sets are generated for X = H, C, N, O, and F, and examined in calculations of linear and nonlinear electric properties of four standard test systems: HF, N₂, CO, and HCN. The study of the performance of LPolX basis sets has been carried out at different levels of approximation ranging from the SCF HF method to highly correlated CCSD(T) approach. The results obtained in this study compare favorably with accurate reference data and show a high level of saturation of LPolX basis sets with respect to the polarization effect due to external electric fields. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Electric dipole,polarizability and structure of cesium chloride clusters with one-excess electron

The measurement of the electric dipole of gas phase one-excess electron Cs_nCl_n−1 clusters is reported together with a theoretical ab initio prediction of stable structures, dipole moments and electronic polarizabilities for these species in their ground state. Results are in agreement with NaCl cubic structures.     

Ab initio calculation of the electronic structure of the strontium hydride ion (SrH+)

The potentials, spectroscopic properties and electric dipole moments of SrH⁺ are computed for 63 molecular states dissociating up to Sr²⁺ + H^? using an ab initio approach. The ab initio formalism is based on large basis sets, nonempirical atomic pseudopotential for strontium core, correlation treatment for core valence through the effective core polarization potentials and for valence through full valence configuration interaction. Our theoretical molecular constants match published values very well and a large amount of new results is produced. Unusual potential shapes are found in ¹Σ⁺ states often caused by avoided crossing series between them and imprinted by the ionic state Sr²⁺H^?. The high potential energy curves suggest, it is possible to form H^? or at least to neutralize H⁺ in collisions with strontium. © 2014 Wiley Periodicals, Inc.     

聚四氟乙烯和聚二甲基硅烷的链尺寸和偶极矩

基于改进的旋转异构态方法,推导了对称双取代基高分子链的均方回转半径和均方偶极矩公式,用于研究聚四氟乙烯(PTFE)、聚二甲基硅烷(PDMS)和聚乙烯(PE)链构象依赖的性质.计算得到长链聚四氟乙烯PTFE4(四态模型)和PDMS的构型参数值分别为0.44·mol0.5·g-0.5和0.43·mol0.5·g-0.5,PDMS链的相应温度系数值-7.32×10-3K-1,它与PTFE和PE的值(约-1.00×10-3K-1)相差较大.得到长链PTFE和PDMS的均方电偶极矩特征比结果都很小,如PDMS链的特征比为0.27,说明虽然PTFE和PDMS的侧基键C—F和Si—CH3都有强极性,但其聚合物却是非极性的电介质,具有较好的电绝缘性能,可见高分子链的构象和结构也对聚合物极性和电学性质有很大的影响.得到短链PTFE和PDMS(重复单元x10)均方偶极矩表现出明显的端点效应,特征比随x的改变而呈现明显的波动,这与Flory等的计算结果一致.     

A Valence Bond Study of the Low‐Lying States of the NF Molecule

The electronic structures of the three lowest‐lying states of NF are investigated by means of modern valence bond (VB) methods such as the VB self‐consistent field (VBSCF), breathing orbital VB (BOVB), and VB configuration interaction (VBCI) methods. The wave functions for the three states are expressed in terms of 9–12 VB structures, which can be further condensed into three or four classical Lewis structures, whose weights are quantitatively estimated. Despite the compactness of the wave functions, the BOVB and VBCI methods reproduce the spectroscopic properties and dipole moments of the three states well, in good agreement with previous computational studies and experimental values. By analogy to the isoelectronic O₂ molecule, the ground state ³Σ^? possesses both a σ bond and 3‐electron π bonds. However, here the polar σ bond contributes the most to the overall bonding. It is augmented by a fractional (19 %) contribution of three‐electron π bonding that arises from π charge transfer from fluorine to nitrogen. In the singlet ¹Δ and ¹Σ⁺ excited states the π‐bonding component is classically covalent, and it contributes 28 % and 37 % to the overall bonding picture for the two states, respectively. The resonance energies are calculated and reveal that π bonding contributes at least 24, 35 and 42 kcal mol^?1 to the total bonding energies of the ³Σ^?, ¹Δ and ¹Σ⁺ states, respectively. Some unusual properties of the NF molecule, like the equilibrium distance shortening and bonding energy increasing upon excitation, the counterintuitive values of the dipole moments and the reversal of the dipole moments as the bond is stretched, are interpreted in the light of the simple valence bond picture. The overall polarity of the molecule is very small in the ground state, and is opposite to the relative electronegativity of N vs F in the singlet excited states. The values of the dipole moments in the three states are quantitatively accounted for by the calculated weights of the VB structures.     

An intramolecular induction correction model of the molecular dipole moment

A model for intramolecular polarization is presented. It is used to describe the changes in the molecular charge distribution occurring as a response to changes of dihedral angles in the molecule. The model is based on a multicenter multipole distribution of the molecular charge distribution. The electric field from this charge distribution induce dipole moments in the same molecule. The model contains atom type parameters to describe the damping of the electric field. A total of four atom types are used. The parameters are fitted to a calibration set with various functional groups, and tested against a validation set. The error obtained for the calibration set is reduced by 92% and by 88% for the validation set, if compared to an accurate state-of-the-art force field. It is shown that rotating the non-polarizable multicenter multipole distribution for the equilibrium geometry gives too large dipole moments for dihedral angles deviating from the equilibrium geometry. This will lead to too large long-range attractions in simulations. This problem is overcome by using the dipole polarizability correction suggested here, which gives dipole moments very close to the Hartree-Fock dipole moments obtained from reference calculations.     

Diaminodicyanoquinones: Fluorescent Dyes with High Dipole Moments and Electron‐Acceptor Properties

Fluorescent dyes are applied in various fields of research, including solar cells and light‐emitting devices, and as reporters for assays and bioimaging studies. Fluorescent dyes with an added high dipole moment pave the way to nonlinear optics and polarity sensitivity. Redox activity makes it possible to switch the molecule's photophysical properties. Diaminodicyanoquinone derivatives possess high dipole moments, yet only low fluorescence quantum yields, and have therefore been neglected as fluorescent dyes. Here we investigate the fluorescence properties of diaminodicyanoquinones using a combined theoretical and experimental approach and derive molecules with a fluorescence quantum yield exceeding 90 %. The diaminodicyanoquinone core moiety provides chemical versatility and can be integrated into novel molecular architectures with unique photophysical features.     

Natural orbital functional approach: Calculation of dielectric properties in molecules

Recently, we proposed a new natural orbital functional for taking into account the electronic correlation in molecular systems. Calculation of dipole moments and polarizabilities of eight selected molecules are presented. By comparison with other correlated methods, it is shown that the method has predictive capabilities for these properties. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Full configuration interaction calculation of the low lying valence and Rydberg states of BeH

The all-electron full configuration interaction (FCI) vertical excitation energies for some low lying valence and Rydberg excited states of BeH are presented in this article. A basis set of valence atomic natural orbitals has been augmented with a series of Rydberg orbitals that have been generated as centered onto the Be atom. The resulting basis set can be described as 4s2p1d/2s1p (Be/H) + 4s4p3d. It allows to calculate Rydberg states up to n= {3,4,5} of the s, p, and d series of Rydberg states. The FCI vertical ionization potential for the same basis set and geometry amounts to 8.298 eV. Other properties such as FCI electric dipole and quadrupole moments and FCI transition dipole and quadrupole moments have also been calculated. The results provide a set of benchmark values for energies, wave functions, properties, and transition properties for the five electron BeH molecule. Most of the states have large multiconfigurational character in spite of their essentially single excited nature and a number of them present an important Rydberg-valence mixing that is achieved through the mixed nature of the particle MO of the single excitations.     

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.     

Charge distribution from a simple molecular orbital type calculation and non-bonding interaction terms in the force field MAB

A simple and fast method to calculate charge distributions in organic molecules is presented. The method is based on charge shifts within the saturated -system, driven by orbital electronegativities, coupled to a modified Hückel treatment of the unsaturated -systems. Experimental molecular dipole moments of a set of 119 molecules are reproduced with a root mean square deviation of 0.36 Debye units. Furthermore, the obtained charge distribution is used to describe hydration free energies in terms of hydrogen-bonding donor and acceptor strengths of polar groups. Least square fitting to experimental data of 281 compounds leads to values for these strengths with accuracy limits of ±4.3% and ±2.5%, respectively. Properly normalized values are taken to parametrize the hydrogen bonding terms in our MAB force field. The method is sufficiently fast to be used in the preparatory phase of interactive force-field calculations.     

Conformational analysis of N-Boc-N,O-isopropylidene-α-serinals. A combined DFT and NMR study

This work describes an extensive conformational analysis of Garner's aldehyde and its α-methylated homologue—two important chiral building blocks that are widely used in organic synthesis. A combination of density-functional theory and NMR spectroscopy confirmed the existence of a dynamic equilibrium between two possible conformers of the carbamate group in these compounds. The calculated properties such as conformer populations and rotational barriers around the (CO)-N bond are in good agreement with the experimental values. Finally, the dipole moments of the molecules appear to be a decisive factor in the stabilization of the conformers in solution.     

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.     

Influence of carbon chain length on physical properties of 3FmHPhF homologues

ABSTRACT

Four compounds from 3FmHPhF homologous series of chiral smectogenic fluorinated compounds (m = 2, 4, 5, 6) were studied by frequency domain dielectric spectroscopy, electro-optic measurements, X-ray diffraction and differential scanning calorimetry. Values of the relaxation time and dielectric increment of relaxation processes versus temperature and bias field were determined. The temperature-dependent tilt angles, spontaneous polarisations, switching times, rotational viscosities, and average intermolecular distances and correlation lengths within smectic layers were obtained. Experimental results were supplemented by density functional theory calculations of isolated 3FmHPhF molecular geometries, and the relationship between the molecular structures and the transverse component of their dipole moments was studied for the mesogens with m = 2, 4, 5, 6, 7. The results are discussed in terms of the length of the C_mH_2m flexible carbon chain of the homologues.     

Improved mesophase stability of benzoxazole derivatives via dipole moment modification

By modifying the molecular dipole moments with lateral monofluorine substituent, improved mesophase stabilities were obtained for novel benzoxazole derivatives, 2-(4?-alkoxy-3-fluorobiphenyl-4-yl)-benzoxazole liquid crystals (coded as nPPF(3)Bx). The series of nPPF(3)Bx with lateral monofluorine substituent ortho to benzoxazole group have larger calculated dipole moments by about 2 D than the corresponding fluorine-substituted analogs (compounds I) with lateral monofluorine ortho to alkoxy group; it is interesting to note that they show lower melting and clearing points but better mesophase stability with wider mesophase ranges for the molecules with both polar (NO₂, Cl) and nonpolar (CH₃, H) terminal groups. Meanwhile, compounds nPPF(3)Bx show greater red-shifted photoluminescence emissions than compounds I, which suggest that π–π interaction between molecules is reinforced by the enhanced dipole–dipole interaction caused by increased dipole moments. These results suggest that modification of the molecular dipole moment is an effective method to improve the mesophase stability of the classical mesogenic compounds.     

Enhanced optoelectronic properties with aromatic bridges: A computational study on N-methyl pyridinium and phenolate types of push-pull zwitterions

A series of zwitterions with varying bridges, connecting N-methyl pyridinium acceptor, with phenolate donor, are investigated using various methodologies like, HF, B3LYP, CAM-B3LYP and ωB97xD. In this systematic study effects of various mono aromatic rings as bridges, on the response properties like, the dipole moments (μ), polarizabilities (α), hyperpolarizabilities (β) and adiabatic absorptions were analyzed using CPHF and TDDFT (or TDHF) theories. Compared to many traditional bridges, as well as without a bridge, enhanced nonlinear optical (2ND order NLO) responses were observed for these aromatically bridged zwitterions (with benzene ring as bridge ~5.3 times and ~7.9 times enhanced hyperpolarizabilities were observed compared to either the ethylene bridge or without any bridge cases, respectively). Also, many significant differences and large enhancements in response properties were observed compared to our earlier works on non-zwitterionic system (~4.3 times enhanced hyperpolarizability—benzene as bridge case). For some bridge cases, 10- to 15-fold enhanced hyperpolarizabilities were observed compared to without any bridge case. This work reports a class of non-TICT chromophores, promoting bridge aromaticity control on structure–property correlation, as a suitable and efficient chromophore design strategy to create a wide range of function molecular chromophores. Also, unidirectional natures of response properties and large dipole moments can make these zwitterions suitable 1D-molecular materials for various contemporary technological applications, as poled polymer-based materials.