Polarisabilites moléculaires et effet diélectrique de milieu à l'état liquide. Étude théorique de la molécule d'eau et de ses diméres

The model of Onsager in which a polar molecule undergoes a reaction field due to the polarization of the molecular surroundings is used to evaluate by a S.C.F. calculation (CNDO/2 approximation) the modifications of a molecular structure in the liquid state.Application to water molecule and to three polar dimers for values of the dielectric constant varying between 3 and 78, shows that most of geometric parameters and dipoles moments vary of few per cent when the molecule is inserted in a liquid. In the liquid state dipole moments do not depend very much on the dielectric constant but energies and relative stabilities of isomers are strongly dependent on the medium.[/p]

     

Differences in the electrorheological response of a particle suspension under direct current and alternating current electric fields

We have observed an unusual reduction of shear stress with increasing shear rate under direct current electric fields, for an electrorheological fluid composed of sulfonated poly(styrene-co-divinylbenzene) particles dispersed in silicone oil. At all shear rates, the shear stress under the electric field is larger than that in the absence of the field, indicating that there is still some field-induced agglomeration of the particles. In contrast, the behavior under alternating current electric fields is the Bingham-fluid-type response commonly observed with electrorheological fluids. It is suggested that the conventional dipole–dipole interaction approach based on simplified microstructural models would be unable to explain these phenomena. Received: 27 November 2000 Accepted: 22 May 2001     

双电层相互重叠时蒙脱胶体表面阴离子的负吸附

本文用Ag-AgCl电极判断平衡,测定双电层处于不同重叠程度下肢体表面阴离子的负吸附量Γ.结果表明,胶体表面双电层相互重叠程度可由两胶体表面间的中点电位φd与外Helmhotz面处的电位φd之比表征;阴离子负吸附随双电层重叠程度和电解质浓度的增加而显著减小.     

Comparison of linear-scaling semiempirical methods and combined quantum mechanical/molecular mechanical methods for enzymic reactions. II. An energy decomposition analysis

QM/MM methods have been developed as a computationally feasible solution to QM simulation of chemical processes, such as enzyme-catalyzed reactions, within a more approximate MM representation of the condensed-phase environment. However, there has been no independent method for checking the quality of this representation, especially for highly nonisotropic protein environments such as those surrounding enzyme active sites. Hence, the validity of QM/MM methods is largely untested. Here we use the possibility of performing all-QM calculations at the semiempirical PM3 level with a linear-scaling method (MOZYME) to assess the performance of a QM/MM method (PM3/AMBER94 force field). Using two model pathways for the hydride-ion transfer reaction of the enzyme dihydrofolate reductase studied previously (Titmuss et al., Chem Phys Lett 2000, 320, 169-176), we have analyzed the reaction energy contributions (QM, QM/MM, and MM) from the QM/MM results and compared them with analogous-region components calculated via an energy partitioning scheme implemented into MOZYME. This analysis further divided the MOZYME components into Coulomb, resonance and exchange energy terms. For the model in which the MM coordinates are kept fixed during the reaction, we find that the MOZYME and QM/MM total energy profiles agree very well, but that there are significant differences in the energy components. Most significantly there is a large change (approximately 16 kcal/mol) in the MOZYME MM component due to polarization of the MM region surrounding the active site, and which arises mostly from MM atoms close to (<10 A) the active-site QM region, which is not modelled explicitly by our QM/MM method. However, for the model where the MM coordinates are allowed to vary during the reaction, we find large differences in the MOZYME and QM/MM total energy profiles, with a discrepancy of 52 kcal/mol between the relative reaction (product-reactant) energies. This is largely due to a difference in the MM energies of 58 kcal/mol, of which we can attribute approximately 40 kcal/mol to geometry effects in the MM region and the remainder, as before, to MM region polarization. Contrary to the fixed-geometry model, there is no correlation of the MM energy changes with distance from the QM region, nor are they contributed by only a few residues. Overall, the results suggest that merely extending the size of the QM region in the QM/MM calculation is not a universal solution to the MOZYME- and QM/MM-method differences. They also suggest that attaching physical significance to MOZYME Coulomb, resonance and exchange components is problematic. Although we conclude that it would be possible to reparameterize the QM/MM force field to reproduce MOZYME energies, a better way to account for both the effects of the protein environment and known deficiencies in semiempirical methods would be to parameterize the force field based on data from DFT or ab initio QM linear-scaling calculations. Such a force field could be used efficiently in MD simulations to calculate free energies.     

Phase separation and disorder in half metallic ferromagnetic manganite thin films: A theoretical study looking forward low noise nano-devices

The resistivity of thin La_0.7Sr_0.3MnO₃ films was first investigated in a wide temperature (T) range (10–750 K). Films grown by different techniques and on several substrates enabled to analyze samples with different amounts of disorder. The aim of this work was to elucidate the nature of the metal–insulator (M–I) transition occurring at T = T_p in these films and its relation with the different kinds of inhomogeneities they could present like intrinsic electric disorder and co-existence of two different electrical and/or magnetic phases. The low-temperature resistivity state was described mostly by a law which scales as T with  ≈ 2.5. This supports the theoretical proposal of single magnon scattering in presence of minority spin states localized by the disorder. In the whole range of temperatures the experimental data are found to be consistent with a phase separation (PS) scenario. In order to go through the origin of the characteristic length scale of inhomogeneity found, preliminarily low frequency noise measurements as a function of T in a range of temperature around the M–I transition were made. The samples used were patterned using photolithography into bridges with various widths and lengths. No clear sign of separation phase dynamic has been observed in our noise measurements. Unexpectedly the normalized Hooge parameter _H/n was found not to be volume (Ω) independent. The LSMO electrical properties may strongly be driven by disorder and new design for magnetoresistance sensors may have to take into account their intrinsic PS.     

On the representation of electrostatic fields around ab initio charge distributions

Summary We compare two methods (Mulliken charges and a distributed multipole analysis, DMA) of representing an ab initio charge distribution for calculating the electrostatic field and potential outside the molecule, using pyrimidine and the RNA base uracil as examples. This is done using a 3-D graphical display of the electrostatic fields, which, when used with real-time rotation, zooming and clipping, has many advantages for qualitatively assessing the electrostatic interactions of a molecule. The errors involved in using Mulliken point charges may be of similar magnitude to the total electrostatic field in regions which are important in recognition processes. The DMA representation automatically includes the anisotropic electrostatic effects of non-spherical features in the charge distribution of each atom, and yet the displayed electrostatic fields around the atoms which have lone-pair density do not show marked anisotropy.     

The inclusion of electrostatic hydration energies in molecular mechanics calculations

Summary The problem of including solvent effects in molecular mechanics calculations is discussed. It is argued that the neglect of charge-solvent (solvation) interactions can introduce significant errors. The finite difference Poisson-Boltzmann (FDPB) method for calculating electrostatic interactions is summarized and is used as a basis for introducing a new pairwise energy term which accounts for charge-solvent interactions. This term acts between all pairs of atoms usually considered in molecular mechanics calculations and can be easily incorporated into existing force fields. As an example, a parameterization is developed for the CHARMm force field and the results compared to the predictions of the FDPB method. An approach to the realistic incorporation of solvent screening into force fields is also outlined.     

Static electric properties of LiH: explicitly correlated coupled cluster calculations

Explicitly correlated MBPT-R12 and coupled cluster [up to CCSD(T)-R12] methods have been used in calculations of various (vibrationless) electrical properties for the LiH molecule, including the dipole and quadrupole moments, dipole and quadrupole polarizability tensors, dipole hyperpolarizability tensors, and the second dipole hyperpolarizability tensors. Generally, with extension of the basis set the R12 method did not lead to faster convergence for the calculated properties towards the basis limit. Nevertheless, R12 calculations serve as useful indicators to judge the reliability of the results, and substantially help in determining the accuracy. Results obtained with the 11s8p6d5f/9s8p6d5f basis and CCSD(T)-R12 calculated within this work should be close to the basis set limit. Received: 8 June 1998 / Accepted: 23 July 1998 / Published online: 7 October 1998     

Inverse Perovskites (Eu3O)E with E = Sn,In – Preparation,Crystal Structures and Physical Properties

The cubic inverse Perovskites (Eu₃O)In and (Eu₃O)Sn were prepared from the metals and Eu₂O₃ or SnO₂, respectively. For (Eu₃O)In the crystal structure analysis was performed on single crystal X‐ray diffraction data (space group , a = 512.79(3) pm, Z = 1, R_gt(F) = 0.022, wR(F²) = 0.044). The data indicated full occupancy on all sites and a fully ordered structure. According to magnetic susceptibility measurements and X‐ray absorption spectroscopic data at the Eu L_III edge both compounds contain europium in the 4f⁷ (Eu²⁺) electronic state. (Eu₃O)In orders ferromagnetically at 185(5) K, (Eu₃O)Sn shows antiferromagnetic order at 31.4(2) K. Both compounds behave as metallic conductors in electrical resistivity measurements. However, (Eu₃O)In may be classified a metal, while (Eu₃O)Sn is more likely a heavily doped degenerated semiconductor or semimetal according to the absolute values of the resistivity.     

Deviation from Ohm's law in electric field assisted capillary liquid chromatography

Earlier studies of electric field assisted LC (EF-LC) have shown that the effect on charged analytes of the application of an electric field over a capillary LC column is relatively small. Charged analytes can only be affected by the electric field while present in the mobile phase, which makes the effective time for influence of the electric field t(0) independent of retention time. Because the charged analytes only can be affected for a short time the electric field strength ought to be high in order to increase the impact of the electric field on the separation. We have, however, found that only a relatively low electric field strength can be used in EF-LC when pressure is used as main driving force. The useful field strength was limited by a dramatic increase in the current. This increase in current was found to origin from an increased concentration of buffer ions that have an electrophoretic mobility towards the pumped flow.