Unraveling σ and π Effects on Magnetic Anisotropy in cis‐NiA4B2 Complexes: Magnetization,HF‐HFEPR Studies,First‐Principles Calculations,and Orbital Modeling

By using complementary experimental techniques and first‐principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C_2v, has been investigated. Four complexes have the general formula [Ni(bpy)X₂]ⁿ⁺ (bpy=2,2′‐bipyridine; X₂=bpy ( 1 ), (NCS^?)₂ ( 2 ), C₂O₄^2? ( 3 ), NO₃^? ( 4 )). In the fifth complex, [Ni(HIM₂‐py)₂(NO₃)]⁺ ( 5 ; HIM₂‐py=2‐(2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM₂‐py. Analysis of the high‐field, high‐frequency electronic paramagnetic resonance (HF‐HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from ?1 to ?10 cm^?1. First‐principles SO‐CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3 , on one hand, and 4 and 5 , on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters (D (axial), E (rhombic), and g_i) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the e_g‐like orbitals and is due to the difference in the σ‐donor strength of NO₃^? and bpy or HIM₂‐py, whereas the difference in anisotropy between the two compounds is due to splitting of the t_2g‐like orbitals; and 2) the anisotropy of complexes 1 – 3 arises from the small splitting of the t_2g‐like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model.     

Stacking Aggregation and Photodimerization of Thymine Chromophores in Aqueous Solutions of Polythymidylic Acid

Optics and Spectroscopy - Heterogeneity of aqueous solutions of polythymidylic acid (poly-T) at room temperature is established by luminescence and absorption spectroscopy. It is found that there...     

Unusual rheological effects observed in polyacrylonitrile solutions

Unusual rheological effects have been revealed during the deformation of polyacrylonitrile (PAN) solutions in DMSO. The effects are observed during the study of rheological properties in a wide range of PAN concentrations and are explained by the structuring occurring at low polymer concentrations. At concentrations of at most 0.1%, the solutions exhibit the behavior of soft gels, which are characterized by yield stresses and frequency-independent storage moduli. As concentration is increased, both effects gradually vanish and the solutions are almost transformed into Newtonian liquids. The results have been explained by the formation of a supramolecular spatial structure at low polymer concentrations. As concentration is increased, the role of structuring is suppressed by the formation of a network of intermacromolecular entanglements. The ability of dilute PAN solutions to exist in two states, i.e., with destroyed structuring and in the form of a physical polymer gel, leads to stress self-oscillations and thixotropic effects. The addition of a precipitant (water) to the PAN-DMSO solutions leads to the formation of a gel throughout the concentration range.     

Powerful Cherenkov oscillators with 2D distributed feedback

The feasibility of using 2D distributed feedback based on 2D planar and coaxial Bragg structures for generating spatially coherent radiation from rectilinear ribbon and tubular electron beams is studied. One-section and sectional Cherenkov masers are analyzed. In the former design, a 2D Bragg structure acts as a resonator and a periodic slow-wave system simultaneously. In the latter (sectional) design, radiation is synchronized in a 2D Bragg structure that is placed at the cathode end of the interaction space and couples longitudinal and transverse (azimuthal) wave flows. The wave is amplified by the electron beam mainly in the fairly long middle section. The output (collector) part contains a standard 1D Bragg structure that partially reflects the amplified radiation toward the cathode and closes the feedback circuit. It is shown that dissipation introduced into the 2D Bragg structure of the sectional design makes it possible to increase one of the transverse sizes of the system to ∼10³ wavelengths with the energy exchange efficiency and one-frequency masing mode stability remaining the same. With such an overdimension, the millimeter-wave radiation integral power may reach a gigawatt level.     

Invariants and radiation of some nonstationary systems

In this paper formulas are obtained by means of the coherent-state method for calculating the radiation power of a nonstationary quantum system ofN charged particles whose Hamiltonian is a general quadratic form with respect to coordinates and momenta. The transitions between the coherent states and the Fock states of this system are discussed. The radiation is calculated both in the dipole approximation and strictly. As an example, the radiation of a charge in homogeneous varying electric and magnetic fields is found. The classical limit is considered.     

PHOTOACOUSTIC SPECTROSCOPY AND RADIANT ENERGY CONVERSION: THEORY OF THE EFFECT WITH SPECIAL EMPHASIS ON PHOTOSYNTHESIS

Abstract—The use of photoacoustic spectroscopy in the study of photoactive samples (photochemical, luminescent, photovoltaic) is considered. After a short explanation of the parameters important in this technique and ways of measuring them, photochemical processes are considered in detail. Relations are derived for the determination of the energy stored in photochemical products and the quantum yield for the photochemical processes.
One- and two-step photochemical processes are treated in detail and the dependence of the photo-acoustically detected products on modulation frequency is considered, showing the possibility of separating reaction steps according to their rate constants. Particular attention is given to the photosynthetic process and the potential of this method for determination of energy conversion efficiencies of the different stages of photosynthesis is demonstrated. Also the use of the technique in the study of photovoltaic processes is outlined.     

Rubber elasticity and viscoelasticity of polymer melts and solutions in shear flow

The principal trends and results of research into the rubbery properties of polymer melts and solutions manifested in shear flow and the relationship between the rubber elasticity and viscoelasticity of these systems are reviewed.     

Some inverse problems in rheology leading to integral equations

Two inverse problems of the integral type, which are of the general importance to rheology, are discussed. The first of them is the possibility of calculating the molecular weight distribution (MWD) from the flow curve and the second one is the interrelation between creep and relaxation functions. It was shown that the first problem is incorrect and any solution is unstable in respect to minor experimental errors. It means that the general solution of this problem is impossible in principle and only estimations of the width of unimodal MWD can be received from the curvature of the flow curve. The possibility of the correct calculation of the creep function exists in case the relaxation curve being approximated by the sum of exponential members. But the approximation of the relaxation curve within the experimental accuracy is the necessary, but not sufficient condition for the correct solution of this integral inverse problem, because not every mode of approximation leads to the satisfactory prediction of creep function.Delivered as the Courtaulds Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.