Mono- and Mixed Metal Complexes of Eu3+, Gd3+, and Tb3+ with a Diketone,Bearing Pyrazole Moiety and CHF2-Group: Structure,Color Tuning,and Kinetics of Energy Transfer between Lanthanide Ions

Three novel lanthanide complexes with the ligand 4,4-difluoro-1-(1,5-dimethyl-1H-pyrazol-4-yl)butane-1,3-dione (HL), namely [LnL₃(H₂O)₂], Ln = Eu, Gd and Tb, were synthesized, and, according to single-crystal X-ray diffraction, are isostructural. The photoluminescent properties of these compounds, as well as of three series of mixed metal complexes [Eu_xTb_1-xL₃(H₂O)₂] (Eu_xTb_1-xL₃), [EuxGd_1-xL₃(H₂O)₂] (Eu_xGd_1-xL₃), and [Gd_xTb_1-xL₃(H₂O)₂] (Gd_xTb_1-xL₃), were studied. The Eu_xTb_1-xL₃ complexes exhibit the simultaneous emission of both Eu³⁺ and Tb³⁺ ions, and the luminescence color rapidly changes from green to red upon introducing even a small fraction of Eu³⁺. A detailed analysis of the luminescence decay made it possible to determine the observed radiative lifetimes of Tb³⁺ and Eu³⁺ and estimate the rate of excitation energy transfer between these ions. For this task, a simple approximation function was proposed. The values of the energy transfer rates determined independently from the luminescence decays of terbium(III) and europium(III) ions show a good correlation.     

Lattice dynamics and phase diagram of aluminum at high temperatures

The dispersion of phonons in the fcc, hcp, and bcc phases of aluminum is calculated at ultrahigh pressures by the method of small displacements in a supercell. The stability of the phonon subsystem is studied. The thermodynamic characteristics are calculated in the quasi-harmonic approximation, and a phase diagram of aluminum is plotted. As compared to the Debye model, the use of a phonon spectrum calculated in the quasi-harmonic approximation significantly broadens the hcp phase field and strongly shifts the phase boundary between the fcc and bcc phases. The normal isentrope is calculated at megabar pressures. It is shown to intersect the fcc-hcp and hcp-bcc phase boundaries. The sound velocity along the normal isentrope is calculated. It is shown to have a nonmonotonic character.     

Tail asymptotics for the supercritical Galton-Watson process in the heavy-tailed case

As is well known, for a supercritical Galton-Watson process Z _n whose offspring distribution has mean m > 1, the ratio W _n := Z _n /m ⁿ has almost surely a limit, say W. We study the tail behaviour of the distributions of W _n and W in the case where Z ₁ has a heavy-tailed distribution, that is, $\mathbb{E}e^{\lambda {\rm Z}_1 } = \infty $ for every λ > 0. We show how different types of distributions of Z ₁ lead to different asymptotic behaviour of the tail of W _n and W. We describe the most likely way in which large values of the process occur.     

New metal chelates of 5-amino-4-azopyrazoles: The crystal and molecular structure of bis{1-phenyl-3-methyl-4-(<Emphasis Type="Italic">p</Emphasis>-tolyl)azo-5-(<Emphasis Type="Italic">p</Emphasis>-carboxymethoxyphenyl)pyrazolamidato}copper(II)

The reactions of 1,3-alkyl(aryl) derivatives of 5-amino-4-azopyrazoles (HL) with copper(2+) acetate afford metal chelates CuL₂. Complexes with the CuN₄ chromophore containing a substituted amino group (X = NR) as a donor, like their azomethine analogues, have a pseudotetrahedral structure. Copper chelates with X = NH are planar. The X-ray diffraction data and an additional hyperfine structure (ahfs) from ¹⁵N atoms of the azo group in the labeled complexes provide evidence for the formation of six-membered metallocycles. The coordination polyhedron in bis{1-phenyl-3-methyl-4-(p-tolyl)azo-5-(p-carboxymethoxyphenyl)pyrazolamidato}Cu(II) can be described as a pseudotetrahedron.     

Influence of size effects on <Emphasis Type="Italic">para</Emphasis>-dichlorobenzene lattice dynamics

We have obtained experimental low-frequency Raman spectra for light scattering by nanoparticles of para-dichlorobenzene of size ∼300–70 nm. As their sizes decrease, the line frequencies decrease. The size of the nanoparticles was determined using an electron microscope. We found that in the lattice vibrational spectrum of nanoparticles of size 300–70 nm, a summed spectrum appears from α-para-dichlorobenzene and β-para-ichlorobenzene. This is consistent with molecular dynamics calculations of the structure of the nanoparticle and calculations of the histograms for the lattice vibrational spectra by the Dean method.     

Magnetic phase diagram of frustrated spin-chain compounds

Generalizations of Glauber dynamics on the triangular lattice of Ising chains are considered. Magnetic moment relaxation and the response to an AC magnetic field in Ca₃Co₂O₆ are investigated. It is shown that all of the main features of the dynamics of a frustrated lattice of spin chains can be described qualitatively in the framework of an extended two-dimensional model.     

Joint free-energy distribution in the random directed polymer problem

We consider two configurations of a random directed polymer of length L confined to a plane and ending in two points separated by 2u. Defining the mean free-energy F[over ] and the free-energy difference F;{'} of the two configurations, we determine the joint distribution function P(L,u)(F[over ],F(')) using the replica approach. We find that for large L and large negative free energies F[over ], the joint distribution function factorizes into longitudinal [P(L,u)(F[over ])] and transverse [P(u)(F('))] components, which furthermore coincide with results obtained previously via different independent routes.     

The reactions of 2H-1,2,3-diazaarsoles with phenyl azide

2-Phenyl-5-methyl- and 2,5-diphenyl-2H-1,2,3-diazaarsoles 1a,b react with phenyl azide to give several crystalline products: tricyclic derivatives 2a,b and 4,4′-bis(2H-1,2,3-diazaarsoles) 5a,b formed at room temperature, and a cycloadduct 6a obtained at +4°C. Compound 6a undergoes a fast rearrangement in solutions of Et₃N or pyridine to give a stable dicoordinate arsenic compound, the 2H-1,2,3-diazaarsole 7a. Heating solutions of 2a under reflux in an inert atmosphere leads to 5a and of 2b, in the presence of water, to 4b. The structures of 2a, 4b, and 7a were characterized by X-ray crystal structure determinations. © 1996 John Wiley & Sons, Inc.     

Study of Complex Effect of Intense Flows of Argon Ions and Pulsed Laser Radiation on Surface of Vanadium and Vanadium-Based Alloys (Review)

Physics of Atomic Nuclei - A review of studies on the effect of intense flows of argon ions and high-power pulsed laser radiation on properties such as microhardness, radiation erosion, structural...