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31.
32.
S. P. Papkov V. G. Kulichikhin V. D. Kalmykova A. Ya Malkin 《Journal of Polymer Science.Polymer Physics》1974,12(9):1753-1770
A study has been made of the viscous properties of poly(para-benzamide) (PBA) solutions in dimethyl acetamide, which undergo a transition from an isotopic to an anisotropic (liquid-crystal) state at a definite concentration C*. The polymer solutions behave in many respects (as regards the concentration and temperature dependence of viscosity, etc.) like solutions of low molecular weight compounds forming a liquid crystal phase, although the transitions are less pronounced in the polymer solutions owing to their polydispersity. It is shown that the viscometric method, being extremely sensitive to C*, is convenient for determining phase diagrams of anisotropic polymer solutions. The values of C* as related to the molecular weight of PBA have been determined, and a general criterion for transition from isotropic to anisotropic solutions established; the latter has the form (CM?)* ≈ 1.3 × 105 at 20°C. This criterion is in line with the condition for the formation of the liquid-crystal structure in a dispersion of rodlike particles as proposed by Flory. Generalized concentration dependences of viscosity have been plotted by reducing concentration to C* and viscosity, to the maximum viscosity at the phase transition point. In investigating the flow properties of PBA solutions we revealed the existence of a yield point in the range of low shear stresses, and an intersection of the flow curves of solutions of different concentration at high shear stresses, which excludes a generalized representation of the flow curves in reduced ordinary-type coordinates. 相似文献
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J. Malkin K. D. Straub A. S Dvornikov P. M. Rentzepis 《Research on Chemical Intermediates》1993,19(2):159-189
The photochemistry, kinetics and spectra of several spiropyran molecules have been studied. The transient species of the photochromic reactions and precursors have been identified and the rate of formation and decay measured. We also present means for the utilization of spiropyrans in writing and accessing information in 3D volume optical memory. 相似文献
36.
L. K. Aminov A. A. Ershova S. L. Korableva I. N. Kurkin A. A. Rodionov B. Z. Malkin 《JETP Letters》2008,87(6):311-315
The observation of the superhyperfine structure (SHFS) in EPR spectra due to enhanced nuclear magnetism is reported. The X-band
spectrum of a U3+ ion introduced into the Van Vleck paramagnet LiTmF4 is measured in the temperature range of 5–20 K and compared with the spectra of LiLuF4:U3+ and LiYF4:U3+ single crystals. The spectra reveal well-resolved and strikingly different SHFS. The SHFS of Li(Lu, Y)F4:U3+ is due to the fluorine ions forming the nearest surroundings of the U3+ ion. The main contribution to the SHFS of the U3+ spectrum in LiTmF4 comes from the Tm3+ ions with a highly enhanced nuclear gyromagnetic tensor.
The text was submitted by the authors in English. 相似文献
37.
Alexander V. Semakov Valery G. Kulichikhin Aleksei K. Tereshin Sergei V. Antonov Alexander Ya. Malkin 《Journal of Polymer Science.Polymer Physics》2015,53(8):559-565
Experiments with stretching moderately concentrated polymer solutions have been carried out. Model experiments were carried out for poly(acrylonitrile) solutions in dimethyl siloxane. Just the choice of concentrated solutions allowed for a clear demonstration of a demixing effect with the formation of two separate phases—an oriented polymer fiber and solvent drops sitting on its surface. An original experimental device for following all subsequent stages in the demixing process was built. It combined two light beams, one transverse to the fiber and a second directed along (inside) the fiber, the latter played the role of an optical line. This gives a unique opportunity to observe processes occurring inside a fiber. The process of demixing starts from the volume phase separation across the whole cross section of a fiber at some critical deformation and the propagation of the front of demixing along the fiber. Then a solvent cylindrical skin appears which transforms into a system of separate droplets. New experimental data are discussed based on a comparison of the current different points of view on the phenomenon of deformation‐induced phase separation: thermodynamic shift of the equilibrium phase transition temperature, growth of stress‐induced concentration fluctuations in two‐component fluids, and mechanically pressing a solvent out from a polymer network. The general belief is that a rather specific (so‐called “beads‐on‐a‐string”) structure of a filament is realized in stretching dilute solutions: beads of a polymer solution connected by oriented polymer bridges forming a single object. The situation in stretching moderately concentrated solutions appears quite different: real phase separation was observed. So, the alternative phenomenon to the formation of the “beads‐on‐a‐string” structure has been experimentally proven. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 559–565 相似文献
38.
Komorovský S Repiský M Malkina OL Malkin VG Malkin Ondík I Kaupp M 《The Journal of chemical physics》2008,128(10):104101
A new relativistic four-component density functional approach for calculations of NMR shielding tensors has been developed and implemented. It is founded on the matrix formulation of the Dirac-Kohn-Sham (DKS) method. Initially, unperturbed equations are solved with the use of a restricted kinetically balanced basis set for the small component. The second-order coupled perturbed DKS method is then based on the use of restricted magnetically balanced basis sets for the small component. Benchmark relativistic calculations have been carried out for the (1)H and heavy-atom nuclear shielding tensors of the HX series (X=F,Cl,Br,I), where spin-orbit effects are known to be very pronounced. The restricted magnetically balanced basis set allows us to avoid additional approximations and/or strong basis set dependence which arises in some related approaches. The method provides an attractive alternative to existing approximate two-component methods with transformed Hamiltonians for relativistic calculations of chemical shifts and spin-spin coupling constants of heavy-atom systems. In particular, no picture-change effects arise in property calculations. 相似文献
39.
Hrobárik P Reviakine R Arbuznikov AV Malkina OL Malkin VG Köhler FH Kaupp M 《The Journal of chemical physics》2007,126(2):024107
The calculation of nuclear shieldings for paramagnetic molecules has been implemented in the ReSpect program, which allows the use of modern density functional methods with accurate treatments of spin-orbit effects for all relevant terms up to order Omicron(alpha4) in the fine structure constant. Compared to previous implementations, the methodology has been extended to compounds of arbitrary spin multiplicity. Effects of zero-field splittings in high-spin systems are approximately accounted for. Validation of the new implementation is carried out for the 13C and 1H NMR signal shifts of the 3d metallocenes 4VCp2, 3CrCp2, 2MnCp2, 6MnCp2, 2CoCp2, and 3NiCp2. Zero-field splitting effects on isotropic shifts tend to be small or negligible. Agreement with experimental isotropic shifts is already good with the BP86 gradient-corrected functional and is further improved by admixture of Hartree-Fock exchange in hybrid functionals. Decomposition of the shieldings confirms the dominant importance of the Fermi-contact shifts, but contributions from spin-orbit dependent terms are frequently also non-negligible. Agreement with 13C NMR shift tensors from solid-state experiments is of similar quality as for isotropic shifts. 相似文献
40.
Batulin R. G. Cherosov M. A. Gil’mutdinov I. F. Khaliulin B. F. Kiiamov A. G. Klekovkina V. V. Malkin B. Z. Mukhamedshin I. R. Mumdzhi I. E. Nikitin S. I. Rodionov A. A. Yusupov R. V. 《Physics of the Solid State》2019,61(5):818-825
Physics of the Solid State - Cubic Y2Ti2O7 single crystals doped with Er3+ or Yb3+ ions have been studied by the methods of electron spin resonance (ESR) and selective laser spectroscopy. ESR... 相似文献