Calculation of the Tautomeric Properties of 3‐Formyl‐Tetrinic Acid by the ab initio and DFT Methods

We have carried out a nonempirical quantumchemical calculation with full optimization of the geometry of all theoretically possible tautomeric forms of 3formyltetrinic acid (FTRA) according to the Møller–Plesset secondorder perturbation theory with the use of a 6–31G(d) double zeta basis set. The correlation corrections to the total energy of molecules for optimized geometric configurations were calculated in the 631G(d,p) basis. All the possible tautomeric forms of FTRA and the harmonic vibrational frequencies were also calculated within the density functional theory (DFT) with the use of the Perdew–Burke–Ernzerhof (PBE) functional in a threeexponent basis. It is shown that FTRA in vapors (in the perfect gas approximation) exists in the form of a mixture of three enol forms, among which two exoforms predominate. The frequencies and forms of normal vibrations for each cisenol tautomer in the region of vibrations of ketogroups and double bonds differ widely, which permits identification of the tautomers present in the mixture. The possible mechanisms of enolenol transformations of 3acyltetrinic acids are discussed.     

Two-dimensional commensurate soliton structures

A phase diagram of pinned soliton structures in two dimensions has been found for a repulsive interactionU(x) between solitons withU(x)>0. The critical fugacity of the commensurate soliton structure is shown to be proportional toU(l), wherel is the period of this structure.     

The maximum entropy principle as a consequence of the principle of Laplace

The maximum entropy principle states that the probability distribution which best represents our information is the one which maximizes the entropy with the given evidence as constraints. We prove that this principle is implied from the Laplace principle of equiprobabilities applied to the setS of allN-term sequences of results which are compatible with the given evidence. We generalize to the information gain method of Kullback.     

Equations for the Magnetization Modes in a System Having a Quadruple Nucleus with the Spin S = 1

Within the framework of the method of a density matrix, differential equations are obtained that describe the evolution of the modes of magnetization <Î₊>, <Î_{+ z} >, and <Î_{+ z} ²> for a spin system containing a nucleus with a 1/2 spin connected scalarly with the quadruple nucleus of the spin S = 1 in the presence of crosscorrelation between the dipole ISinteractions, anisotropy of the chemical shift of the I and S nuclei, and quadruple interaction of the S nucleus. The equations are used for analysis of the evolution of the intensities of each line in the triplet of the Raman spectrum of the 1/2 spin. Expressions for the times of crossrelaxation and the times of transverse relaxation of each of the lines of the triplet are obtained.     

Gas‐Kinetic Temperature of Planar High‐Frequency Capacitive Discharge Plasma in N2/CO2/He Gas Mixtures

Using methods of emission spectroscopy, we have determined the gaskinetic temperature fields of planar highfrequency capacitive discharge plasma in N₂/CO₂/He gas mixtures depending on the excitation frequency, discharge current, pressure, and chemical composition of the mixture. It is shown that the dominant contribution to the neutral component heating in the center of the discharge chamber is made by the processes of V–T relaxation of vibrationally excited molecules N₂(X ¹, V) and CO₂(X ¹, V), whereas in the zones near the electrodes an important role in the heating is played, along with the V–T relaxation of the N₂(X ¹, V) and CO₂(X ¹, V) molecules, by the processes of deactivation of the metastable states A ³ of the N₂ molecule.     

On the efficiency of small-angle Čerenkov second harmonic generation in optical waveguides

It is well known that in the non-depleted pump approximation, the efficiency of a second harmonic generation (SHG) of a guided mode in a non-linear optical waveguide increases quadratically with the interaction length (P ₂ L ²), and linearly (P ₂ L) in the erenkov regime. The efficiency of the erenkov SHG in the waveguide with a non-linear substrate and linear guiding layer is known to be strongly peaked at a particular pump wavelength and a particular waveguide thickness, with the erenkov angle approaching zero. The known theory predicts an infinite efficiency value at the peak, however. In this contribution, a simple integral expression for the SHG efficiency in the erenkov regime is derived. For large erenkov angles and interaction lengths it yields the expected P ₂ L dependence, while in the limit of small erenkov angles the dependence is found to have the form of P L ^3/2, possessing also a finite value at the efficiency peak. The condition determining the accurate position of the efficiency peak in the waveguide thickness–pump wavelength plane is given, too.     

Monte Carlo study of the ising model phase transition in terms of the percolation transition of “physical clusters”

Finite squareL×L Ising lattices with ferromagnetic nearest neighbor interaction are simulated using the Swendsen-Wang cluster algorithm. Both thermal properties (internal energyU, specific heatC, magnetization |M|, susceptibility) and percolation cluster properties relating to the physical clusters, namely the Fortuin-Kasteleyn clusters (percolation probability P , percolation susceptibility _p, cluster size distributionn _l) are evaluated, paying particular attention to finite-size effects. It is shown that thermal properties can be expressed entirely in terms of cluster properties, P being identical to |M| in the thermodynamic limit, while finite-size corrections differ. In contrast, _p differs from even in the thermodynamic limit, since a fluctuation in the size of the percolating net contributes to, but not to _p. NearT _c the cluster size distribution has the scaling properties as hypothesized by earlier phenomenological theories. We also present a generalization of the Swendsen-Wang algorithm allowing one to cross over continuously to the Glauber dynamics.     

Preparation, Luminescence Properties, and Application of Scintillators Based on Lu3Al5O12:Ce Single‐Crystal Films

The possibility of obtaining scintillators with a high effective atomic number of the element Z _ef based on Lu₃Al₅O₁₂:Ce³⁺ singlecrystal films (SCF) on doping with La³⁺ and Sc³⁺ ions on Y₃Al₅O₁₂ substrates has been investigated. It is established that the SCF of (LuLaY)₃Al₅O₁₂:Ce³⁺ (Z _ef = 58.9 and = 6.67 g/cm²) does not rank below those of Y₃Al₅O₁₂:Ce³⁺ (Z _ef = 29 and = 4.52 g/cm²) in the conversion efficiency of radiation at the band with _max = 515 nm. This allows their use as screens of xray images with a space resolution of 0.75–1.00 m. It is suggested that in the SCF of Lu₃Al₅O₁₂ the isoelectronic impurities of lanthanum and scandium form radiative recombination centers of the type La_Lu, Sc_Lu, and ScAl as well as the centers Lu as a consequence of the effect of replacement of some Lu³⁺ ions by the La³⁺ ions to octanodes of the garnet lattice. The low efficiency of Ce³⁺ radiation in the SCF of (LuSc)₃(AlSc)₅O₁₂:Ce is explained by substantial losses due to excitation of the recombination luminescence in the UV region of the centers formed by the isoelectronic impurities of scandium and to the possible existence of the channel of energy excitation dissipation related to the transitions between extrema of the allowed energy bands and activator levels.     

Proton-neutron configurations in 236g, mAm and its EC-decay daughter 236Pu

The EC decay of ²³⁶Am has been studied using a gas-jet coupled on-line isotope separator. A half-life analysis revealed that there are two EC-decaying states in ²³⁶Am: the 5^- state with T_1/2 = 3.6(2) min and the (1^-) state with T_1/2 = 2.9(2) min. The 1185.5 keV level in ²³⁶Pu was found to be the K isomer with K = 5^- and t_1/2 = 1.2(3) s. EC transitions from ^{236g, m}Am to the 1185.5, 1311.5, and 1340.8 keV levels in ²³⁶Pu show small log ft values of 4.9, 5.3, and 4.8, respectively, indicating that the 5/2⁺[642] 5/2⁺[633] transition largely contributes to these transitions, and thus, the populated levels should be the 5/2^-[523]5/2⁺[642] two-quasiparticle states. The K = 0^- octupole band established in ²³⁶Pu is located at higher energy than those in ^238,240Pu, which implies that the octupole correlations become weak at ²³⁶Pu.     

EC and α decays of 235Am

EC and decays of ²³⁵Am have been studied using a gas-jet coupled on-line isotope separator. Excited states in ²³⁵Pu have been established for the first time by means of -ray spectroscopy following the EC decay of ²³⁵Am. The deduced log ft value suggests that the ground state of ²³⁵Am should have the 5/2^-[523] configuration. The - coincidence result has revealed that the 5/2^-[523] state in ²³¹Np populated by the favored transition of ²³⁵Am is located at < 15 keV, which allows us to precisely determine the Q value of ²³⁵Am.     

Luminescence of Trivalent Thulium Ions in Complexes with β-Diketones

It is established that a fairly intense luminescence of thulium can be observed in solutions (suspensions of residues) of different-ligand complexes that include -diketone and an organic base. The luminescence characteristics of Tm compounds are determined in the series of acetyl acetone derivatives with different substituents, including fluorinated ones, of different length and structure. A relationship is found between I, , and of the Tm complexes and the character of the substituents in a -diketone molecule.     

Spectral‐Luminescence Characteristics of Polyphenyls and Polyacenes in the Gas Phase in Electron‐Beam Excitation

The spectra of electronenergy loss, excitation functions, and fluorescence spectra in excitation of the vapor of polyphenyls and polyacenes by electron beams of different energies are determined. The influence of successive complication of the molecules under study on these spectralluminescence characteristics is tracked. Unlike the optical absorption spectra, in the spectra of electronenergy loss of all the substances studied one observes a band which is related to the singlettriplet transition S ₀–T ₁. The transitions up to S ₀–S ₅ are recorded in excitation of the molecules by highenergy electrons, including the region of vacuum ultraviolet. From the functions of fluorescence excitation the authors have determined the excitation thresholds that correlate with the energies of the S ₁ levels, except for pyrene in which the S ₀–S ₁ transition is forbidden and does not show up not only in photon excitation but also in electronbeam excitation, although the intercombination forbiddenness in the latter case is removed and the S ₀–T ₁ band is observed.     

Optical Pumping of Samarium Atoms in a Bichromatic Laser Field in the Presence of Velocity-Changing Collisions

Dark resonances in the ¹⁵⁴Sm -system 4f ⁶6s ²(⁷ F ₀) 4f ⁶6s6p(⁹ F ₁ ⁰) 4f ⁶ s ²(⁷ F ₁) are observed alongside the velocity selective optical pumping. The shape of the resulting spectra strongly depended on the buffer gas (He, Ar) pressure due to velocity-changing collisions (VCC): the sign of the effect could be reversed from the dark to the bright resonance. The observed spectra are interpreted within the framework of the hard-sphere collision model. The role of VCC in the formation of the dark state in the -system is discussed.     

Calculation of Out‐of‐Plane Vibrations of a Porphin Molecule

Using the DFT/B3LYP method with the base set 631G^**, we carried out calculation of the frequencies of the normal vibrations of porphin and of its five isotopic types. Scaling of force constants for outofplane vibrations has been performed in independent natural coordinates. The symmetry coordinates are introduced and a force field for outof plane vibrations of a porphin molecule in independent coordinates of symmetry is obtained. A new correlation of the frequencies of vibrations in the type of the symmetry B _1u for the isotopic type of the d ₂ porphin molecule is suggested on the basis of discrete analysis of the distribution of a potential energy.     

O(N) vector model with twisted boundary conditions

Prompted by a recent article of Chakravarty, we reexamine theO(N) vector model with twisted boundary conditions ind dimensions in the various frameworks of the =d–2 expansion, the =4–d expansion, and the large-N expansion. These continuum models describe the physics below the critical temperatureT _c and nearT _c of a latticeO(N) spin model. We determine the effect of the twisting on finite-size scaling functions, for various geometries.On leave from G. Nadjakov Institute of Solid State Physics, 1784 Sofia, Bulgaria.     

Time-Dependent Vacuum Energy Induced by {\mathcal{D}}–Particle Recoil

We consider cosmology in the framework of a material reference system of particles, including the effects of quantum recoil induced by closed-string probe particles. We find a time-dependent contribution to the cosmological vacuum energy, which relaxes to zero as 1/t ² for large times t. If this energy density is dominant, the Universe expands with a scale factor R(t)t ². We show that this possibility is compatible with recent observational constraints from high–redshift supernovae, and may also respect other phenomenological bounds on time variation in the vacuum energy imposed by early cosmology.     

Finite-size effects in a field-theoretic model with long-range exchange interaction

We present a systematic approach to the calculation of finite-size (FS) effects for anO(n) field-theoretic model with both short-range (SR) and long-range (LR) exchange interactions. The LR exchange interaction decays at large distances as 1/r ^d+2–2,0⁺,0⁺. Renormalization group calculations ind=d _u – are performed for a system with a fully finite (block) geometry under periodic boundary conditions. We calculate the FS shift of the critical temperature and the FS renormalized coupling constant of the model to one-loop order. The universal scaling variable is obtained and the FS scaling hypothesis is verified.     

Interfacial free energies and solute diffusivities from data on Ostwald ripening

Using recent theoretical modifications of the kinetic constants characterizing Ostwald ripening, it is demonstrated that accurate values of the interfacial free energy, , and solute diffusivities, D, can be obtained from experimental data when the kinetics of particle growth are measured in conjunction with independent measurements of either the decrease of the matrix supersaturation or the increase in volume fraction with aging time. The accuracy of is limited only by the assumption that the matrix phase is an ideal solid solution, and is effectively independent of the influence of equilibrium volume fraction, _e, on the kinetics of coarsening. Analyses of the available data on the coarsening of -type (Ni₃X) precipitates in binary Ni–Al, Ni–Si and Ni–Ti alloys yield values of =6.9±0.3, 10.2±3.0 and 13.0 mJ/m², respectively, assuming ideal solution thermodynamics; a more realistic thermodynamic model for the Ni–Al solid solution raises the value of in Ni–Al alloys to 8.1±0.2 mJ/m². Proportional increases probably obtain in the other two alloys. The accuracy with which D can be evaluated from comparable data depends theoretically on _e. However, analyses of the same data yield values of D in very good agreement with the results of conventional diffusion experiments. This is consistent with the absence of an effect of _e on the kinetics of Ostwald ripening in these alloys over the ranges of _e investigated.     

The βdecay of 147Cs to 147Ba

The ^--decay of ¹⁴⁷Cs to ¹⁴⁷Ba has been studied by means of - and X-ray spectroscopy. A new level scheme of ¹⁴⁷Ba is significantly modified and extended in comparison to the one previously reported. The Advanced Time-Delayed (t) method has been applied to measure half-lives of the 46.2 and 85.4 keV levels in ¹⁴⁷Ba yielding T_1/2 of 510(80) ps and 370(100) ps, respectively. The lifetime results combined with the deduced internal conversion coefficients allowed to assign M1 multipolarity to three transitions. The B(M1) values obtained for the 39.2, 46.2 and 85.4 keV transitions range from 0.017 to 0.043 W.u. and represent typical B(M1) strength in the Ba-Er region. Model calculations using a shell correction approach with the axially deformed Woods-Saxon potential predict for ¹⁴⁷Ba an octupole deformed ground state with ₃ = 0.11.     

K-forbidden allowed $ \beta$ transitions in heavy nuclei

The role of the band quantum number K in influencing the character of allowed transitions in heavy deformed nuclei is examined. The conditions for the occurrence of K -forbidden decays in this region are explored. Specific cases of “allowed” decays proceeding via K = 2 to K = 6 channels are presented to illustrate the phenomenon. The listed K = 2 transitions, which by themselves contribute over 10% of all the presently known allowed transitions for A 228 nuclei, are seen to have an average , which is clearly outside the normal range for allowed transitions. It is concluded that, wherever the -connected states can be confidently labelled using the quantum numbers, the K -forbiddenness is in general as significant as that involving the other two (spin and parity) quantum numbers.