Effects of chelation on the interaction of substituted 3-hetaryl-4-thioxochromones with lanthanide shift reagents

Unusual cases of effective coordination of substituted 4-thioxochromones with lanthanide shift reagents have been studied. It is shown that the necessary condition for such coordination is the presence in the 3-hetaryl substituent of a pyridine type nitrogen atom next to the bond between the heterocyclic fragments. Coordination with the lanthanide shift reagents is explained by the formation of chelates of the shift reagents with substrate molecule. Calculations on the structures of these complexes have been carried out.Taras Shevchenko Kiev University, Ukraine; e-mail: ovl@bhf2.kiev.ua. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, 605–610, May, 2000.     

13C NMR Study of Ethylene/propylene/octene-1Terpolymers Synthesized with TiCl4/MgCl2/I-Bu3Al as the Catalyst

Introduction　　 Various ethylene/ α- olefin copolymers such as LLDPE,VLDPE/ ULDPE,EPR,EPDMetc.have a wide application in polymer materials science and engineering.The properties ofthose copolymers are greatly influenced by the type,content and distributions of thecomonomer branches.The effects of different kinds of chain branches,which were derivedfrom comonomerincorporationsin themain chain of the ethylene/α- olefin copolymers on theirproperties and studied by many authors,have sh…     

Spectral-luminescent properties and photoinduced transformations of bisanthene and bisanthenequinone

Based on the study of photochemical transformations of bisanthene in oxygen-containing solutions, it was established that the final product of this reaction is bisanthenequinone. It is shown that in the course of this oxidation reaction the intermediate compounds endomonoperoxide and bisanthene endobiperoxide are formed. Quantum-chemical calculation of the geometrical structure and electronic spectra of the endoperoxides has shown that they have a nonplanar structure, and their absorption spectra experience a large hypsochromic shift. The absorption and fluorescence spectra of solutions of bisanthene in different solvents at 300 and 77 K were investigated. The large Stokes shift of the fluorescence spectra of the solutions of bisanthene in benzene and in its methyl derivatives is explained by the action of intermolecular interactions. The quasi-line fluorescence spectra of solutions of bisanthene in the matrices of saturated hydrocarbons were recorded. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 2, pp. 176–182, March–April, 2000.     

Spectrum of Radiation Transmission by a Thin Layer of Resonant Atoms

We have explored the possibility of observing bistability of the frequency dependence of transmission of a thin (less than the wavelength of the acting laser radiation) surface layer of active atoms. For the external field strength corresponding to the transition saturation, we predict the hysteresis behavior of transmission on separate portions of the dependence and sharp asymmetry of resonance curves of absorption if the influence on the dielectric constant of the medium of a layer of transitions adjacent to the resonance one and capable of interacting with radiation is taken into account.     

兰姆移位的一种半定量计算方法

考虑一个自由电子以动量p运动时因吸放虚光子而引起自能的辐射修正,用非协变形式的量子微扰论算出它有b₂p⁴的形式.在此基础上加上真空极化修正和核有限半径引起的修正,算得氢原子2S_1/2–2P_1/2态的兰姆移位为1056.522MHz,比实验值1057.845MHz仅小0.13%. 用Dirac方程作相对论性修正后,还计算了氢原子4D_5/2–4S_1/2态的能级差,所谓“超兰姆移位”和1S态的“绝对”兰姆移位.误差最大达6.7%,并分析了原因.     

Mechanism for the Correlated Swinging of Photoluminescence Intensity and Peak Energy Shift with Sizes of Nanoscale Si Particles

Based on the quantum confinement-luminescence center model, we focus on the relationship between the photoluminescence (PL) spectra and sizes of nanoscale silicon particles.We find that when there are two kinds of luminescence centers (LC) in the oxide layer surrounding the silicon particles, both the integrated PL intensity and the spectral peak position swing with reducing the sizes of silicon particles, which is different from the monotonous blueshift of peak position predicted by quantum confinement model. By changing the concentrations of LC we find the correlation between the spectral peak position and the integrated PL intensity when the size of silicon particles is reduced. The effects of other parameters such as the half width of size distribution and the position of photon emission levels of LC are also found to be important.     

Bohr–Weisskopf effect: influence of the distributed nuclear magnetization on hfs

Nuclear magnetic moments provide a sensitive test of nuclear wave functions, in particular those of neutrons, which are not readily obtainable from other nuclear data. These are taking added importance by recent proposals to study parity non-conservation (PNC) effects in alkali atoms in isotopic series. By taking ratios of the PNC effects in pairs of isotopes, uncertainties in the atomic wave functions are largely cancelled out at the cost of knowledge of the change in the neutron wave function. The Bohr–Weisskopf effect (B–W) in the hyperfine structure interaction of atoms measures the influence of the spatial distribution of the nuclear magnetization, and thereby provides an additional constraint on the determination of the neutron wave function. The added great importance of B–W in the determination of QED effects from the hfs in hydrogen-like ions of heavy elements, as measured recently at GSI, is noted. The B–W experiments require precision measurements of the hfs interactions and, independently, of the nuclear magnetic moments. A novel atomic beam magnetic resonance (ABMR) method, combining rf and laser excitation, has been developed for a systematic study and initially applied to stable isotopes. Difficulties in adapting the experiment to the ISOLDE radioactive ion beam, which have now been surmounted, are discussed. A first radioactive beam measurement for this study, the precision hfs of ¹²⁶Cs, has been obtained recently. The result is 3629.515(∼0.001) MHz. The ability of ABMR to determine with high precision nuclear magnetic moments in free atoms is a desideratum for the extraction of QED effects from the hfs of the hydrogen-like ions. We also point out manifestations of B–W in condensed matter and atomic physics. This revised version was published online in July 2006 with corrections to the Cover Date.     

Absorption and emission properties of 5-phenyl tris(8-hydroxyquinolinato) M(III) complexes (M = Al,Ga, In) and correlations with molecular electrostatic potential

Substituent effect for a series of 5-phenyl tris(8-hydroxyquinolinato) M(III) complexes (Mq3) of aluminum, gallium, and indium are investigated using density functional theory (DFT) for the ground state properties and the time-dependent version of DFT (TDDFT) for their absorption and emission properties. A comparison between the ground state energy of mer and fac isomers of all the complexes revealed that the mer configuration is always more stable than fac. The substituent effect is significantly reflected at the fluorescence maximum (λ_F) values whereas the effect is moderate at the absorption maximum (λ_abs) values. The molecular electrostatic potential (MESP) at the metal center (V_M) and the most electron rich region indicated by MESP minimum (V_min), located at the oxygen of phenoxide ring exhibit excellent correlations with the λ_F and Stokes shift (λ_F−λ_abs) values. The study suggests the use of Stokes shift as an experimental quantity to measure the excited state substituent effect while the V_min or V_M emerge as theoretical quantities to measure the same.     

Thermally assisted magnetic recording with bit-patterned media to achieve areal recording density beyond 5 Tb/in

Thermally assisted magnetic recording (TAR) with bit-patterned media was investigated by micromagnetic simulation. The media were assumed to be FePt layers. The effective head-field margin as well as the increase in temperature margin and down-track shift margin was investigated. Conditions of the head and medium that lead to a recording density beyond 5 Tb/in² were proposed.