Quantum yield and rate constant of the singlet <Superscript>1</Superscript>Δ<Subscript><Emphasis Type="Italic">g</Emphasis></Subscript> oxygen luminescence in an aqueous medium in the presence of nanoscale inhomogeneities

The quantum yields and lifetimes of photosensitized luminescence of the ¹Δ _g state of singlet oxygen in an aquatic media with a controlled concentration of dielectric anisotropy centers (polyethylene glycol) have been measured using the methods of laser fluorometry. It is established that the quantum yield and the rate constant (k _r ) of the a ¹Δ _g → X ³Σ _g ^- luminescence of ¹O₂ increase as the polymer concentration increases. The effect is analyzed within a general approach involving a relationship between kr and dielectric properties of the medium and is explained by the increased density of photon states and the local field factor in the space around O₂(а ¹Δ _g ).     

Vibronic-spin-orbit interactions in heterocyclic analogues of fluorene with the N and O heteroatoms

The transition dipole moments P _0n ^s for the transitions from the electronic triplet state ³ B ²(ππ*) to vibrational sublevels of the vibrational out-of-plane modes n of the carbazole and dibenzofuran molecules are calculated. The values of the radiative deactivation rate constant k _rad ^s of the triplet sublevels T ^s are determined along with the components k _SO ^s and k _VSO ^s of this constant, which depend on the intramolecular spin-orbit (SO) and vibronic-spin-orbit (VSO) interaction. It is ascertained that k _rad ^z > k _rad ^y . For different structural units of the molecules (the heteroatom and the carbon atoms of the dibenzene fragment), the effect of the SO coupling on the constant k _VSO～Σ_{s, n} (P _0n ^s )² is studied. A competition between the effects on k _VSO from the SO coupling in the carbon atoms and in the light N and O heteroatoms is revealed. This competition accounts for the weak influence of the heteroatom on this component of the rate constant k _rad in these molecules. It is ascertained that the intensity distribution among the vibronic lines in the phosphorescence spectra of carbazole and dibenzofuran I _0n ～Σs (P _0n ^s )² is different due to the substantially different influence of the N and O heteroatoms on the deactivation of the triplet sublevel T ^y .     

Optical characteristics of radiation from N<Stack><Subscript>2</Subscript><Superscript>*</Superscript></Stack> dimers in a barrier discharge

The spectral and power characteristics of radiation of the second positive system of nitrogen (C ³Π _u → B ³Π _g ) in Ar-N₂ and Ar-N₂-Cl₂ mixtures excited by barrier discharge have been studied experimentally. Addition of argon to N₂ increased the radiation power by sixfold. In the triple mixture Ar-N₂-Cl₂ = 210/0.5/0.005, minor chlorine additions increased the intensity of the C ³Π _u → _B ³Π _g transition by 26% compared to Ar-N₂ mixtures. Radiation power density of 2.7 mW/cm² has been achieved. In both binary and triple mixtures, the second positive system of nitrogen was the major contributor to radiation, while the contributions of the fourth positive system of N ₂ ^* (D ³Σ _u ⁺ → B ³Π _g ), the Vegard-Kaplan transition of N ₂ ^* (A ³Σ _u ⁺ → X ¹Σ _g ⁺ ), and the D′ → A′ band of Cl ₂ ^* were negligibly small.     

Formation of the incommensurate ordered phase in TaC<Subscript>y</Subscript> carbide

Structural neutron diffraction studies indicate that only one ordered phase arises after the disorder-order transition in nonstoichiometric cubic tantalum carbide TaC_y. This phase arises in the composition range y = 0.79–0.89 due to long-term annealing with a decrease in temperature from 1600 to 300 K. It is incommensurate in the [1–11]_B1 direction, but it is close to commensurate M₆C₅ structures (C2/m and P3₁ space groups) in mutual arrangement of atoms and vacancies in nonmetallic (1–11)_B1 planes. The disorder-order transition channel that is associated with the formation of the incommensurate superstructure in TaC_y carbide includes two arms k ₅ ⁽⁶⁾ ≈ 0.473b₂ and k ₅ ⁽⁵⁾ = ?k ₅ ⁽⁶⁾ of the {k₅} star and arms of the {k₄} and {k₃} stars. The translation period of the incommensurate phase in the [1–11]_B1 direction is 8.9–9.1 nm, which is larger than that in the commensurate phase M₆C₅ by a factor of about 18.     

Dipole moment functions for electronic transitions from ion-pair states of the second tier of molecular iodine

The emission spectra caused by the transitions from the ion-pair states and f0 _g ⁺ and G1_g of the I₂ molecule are obtained by excitation of individual rovibronic levels of the molecule by the method of optical-optical double resonance. The emission spectra from the state F0 _u ⁺ populated due to collisions I₂(f) + I₂(X) are also measured. By modeling the experimental emission spectra, the dipole moment functions for the electronic transitions f _g ⁺ -B0 _u ⁺ , A0 _u ⁺ , and B″0 _u ⁺ ; G1_g-A0 _u ⁺ and B″0 _u ⁺ ; and F0 _u ⁺ -X0 _g ⁺ and a′0 _g ⁺ of the iodine molecule are reconstructed.     

Refinement of the hadronic contribution to the muon anomalous magnetic moment and to α(<Emphasis Type="Italic">M</Emphasis><Stack><Subscript>z</Subscript><Superscript>2</Superscript></Stack>)

The contribution of the muon anomalous magnetic moment aμ(hadr) to the vacuum polarization and electro-magnetic coupling constant α(q²) for q²=M _z ² is refined by using a new, more accurate value of the ρ-meson width. The values aμ(hadr)=678(7)×10^?10 and δα(M _z ² =0.02786(6) were obtained in a QCD model with an infinite number of vector mesons.     

On combustion enhancement mechanisms in the case of electrical-discharge-excited oxygen molecules

Combustion intensification mechanisms in a supersonic flow of a hydrogen-oxygen mixture behind the oblique shock wave front are investigated for the case when vibrations and the a ¹Δ_g and b ¹Σ _g ⁺ electron states of a O₂ molecule are excited by an electrical discharge. The presence of vibrationally excited and electronically excited O₂ molecules in the oxygen plasma allows intensification of the chain mechanism in the H₂-O₂ mixture even if the energy put into O₂ molecules in the discharge is low. Excitation of O₂ molecules is several tens of times more efficient for acceleration of oxygen-hydrogen mixture combustion than mere heating of the gas by an electrical discharge. In addition, low-temperature inflammation of the mixture with electrical-discharge-excited O₂ molecules makes it possible to raise the efficiency of conversion of the reactant chemical energy to heat compared with the conventional way of combustion initiation by heating.     

Fluorescence quenching of vaporous polycyclic aromatic hydrocarbons by oxygen

The fluorescence quenching by oxygen of vapors of nine polycyclic aromatic hydrocarbons with strongly different oxidation potentials 0.44 eV < E _ox < 1.61 eV (anthracene, 9-methylanthracene, 2-aminoanthracene, 9,10-dibromanthracene, pyrene, chrysene, phenanthrene, fluoranthene, and carbazole) is studied. From the dependences of the fluorescence decay rates and intensities on the oxygen pressure P _O2, the quenching rate constants k _S ^O2 for the excited singlet states S ₁ and the fraction f _S ^O2 of the S ₁ states quenched by oxygen are estimated. At P _O2 = 5 Torr, the k _S ^O2 constants vary from 1.2 × 10⁷ to 3.0 × 10⁵ s^?1 Torr^?1, while the fraction of the quenched excited singlet states changes from 0.1 (fluoranthene) to 0.7 (chrysene) and 0.8 (pyrene). The dependences of k _S ^O2 on the photophysical and electron-donor characteristics of the fluorescing compounds are analyzed. It is shown that, in the gas phase of anthracene and its derivatives, the magnitudes of k _S ^O2 are limited by the rate constants of gas-kinetic collisions k _gk and do not depend on the electron-donor characteristics of fluorophores, while the fraction of quenched states f _S ^O2 changes with the oxidation potential. For compounds with k _S ^O2 < k gk, both the rate constants k _S ^O2 and the fraction of quenched states f _S ^O2 depend on the E _ox of sensitizers, which demonstrates an important role played by the charge-transfer interactions in quenching of the S ₁ states. The dependence of the rate constants k _S ^O2 on the free energy of electron transfer ΔG _et is considered.     

Effect of the Lattice and Spin-Phonon Contributions on the Temperature Behavior of the Ground State Splitting of Gd<Superscript>3+</Superscript> in SrMoO<Subscript>4</Subscript>

The temperature behavior of the EPR spectra of the Gd³⁺ impurity center in single crystals of SrMoO₄ in the temperature range T = 99–375 K is studied. The analysis of the temperature dependences of the spin Hamiltonian b ₂ ⁰ (T) = b₂(F) + b₂(L) and P ₂ ⁰ (T) = P₂(F) + P₂(L) (for Gd¹⁵⁷) describing the EPR spectrum and contributing to the Gd³⁺ ground state splitting ΔE is carried out. In terms of the Newman model, the values of b₂(L) and P₂(L) depending on the thermal expansion of the static lattice are estimated; the b₂(F) and P₂(F) spin-phonon contributions determined by the lattice ion oscillations are separated. The analysis of b ₂ ⁰ (T) and P ₂ ⁰ (T) is evidence of the positive contribution of the spin-phonon interaction; the model of the local oscillations of the impurity cluster with close frequencies ω describes well the temperature behavior of b₂(F) and P₂(F).     

The Structure of Radiative Tunnel Recombination Sites in Emulsion Microcrystals of AgBr(I)

To identify the structure of emissive tunnel recombination sites in the emulsion microcrystals of silver bromide AgBr(I) with iodine contaminations and to determine the role of an emulsion medium in their formation, the temperature dependence of the luminescence spectra in the range from 77 to 120 K, the kinetics of the growth of the maximum luminescence intensity value at λ ≈ 560 nm, and the luminescence flash spectrum stimulated by the infrared light are investigated. Two types of the AgBr_{1 – x}(I _x ) (x = 0.03) microcrystals—namely, obtained in an aqueous solution and on a gelatin substrate—are used in the studies. It is established that the emissive tunnel recombination sites with a luminescence maximum at λ ≈ 560 nm in AgBr_{1 – x}(I _x ) (x = 0.03) are the {(I _a ^- I _a ^- )Ag _i ⁺ } donor–acceptor complexes with the I _a ^- iodine ions located in neighbor anionic sites of the AgBr(I) crystal lattice, next to which the Ag _i ⁺ interstitial silver ion is positioned. With an increase in the temperature, the {(I _a ^- I _a ^- )Ag _i ⁺ } sites undergo structural transformation into the {(I _a ^- I _a ^- )Ag_in⁺} sites, where n = 2, 3, …. Moreover, the {(I _a ^- I _a ^- )Ag _in ⁺ } sites (n = 2) after the capture of an electron and hole also provide the tunnel recombination with a luminescence maximum at λ ≈ 720 nm. The influence of an emulsion medium consists in that gelatin interacts with the surface electron-localization sites, i.e., the interstitial silver ions Ag _in ⁺ , n = 1, 2, and forms the complexes {Ag _in ⁰ G⁺} (n = 1, 2) with them. The latter are deeper electron traps with a small capture cross section as compared to the Ag _in ⁺ sites (n = 1, 2) and that manifest themselves in that the kinetics of the luminescence growth in AgBr(I) to a stationary level at λ ≈ 560 nm is characterized by the presence of “flash firing.” At the same time, the luminescence flash stimulated by IR light, for which the Ag _in ⁺ (n = 1, 2) electron-localization sites are responsible, is absent. It is supposed that the electrons localized on the {Ag _in ⁺ G⁺} complexes (n = 2) retain the capability for emissive tunnel recombination with holes localized on paired iodine sites with a luminescence maximum at λ ≈ 750 nm.     

High-frequency EPR of Cr<Superscript>2+</Superscript> ions in CdGa<Subscript>2</Subscript>S<Subscript>4</Subscript>

High-frequency broad-band (65–240 GHz) EPR is used to study impurity centers of bivalent chromium in a CdGa₂S₄ crystal. It is found that the EPR spectra correspond to tetragonal symmetry. The spin Hamiltonian H = βB · g · S + B ₂ ⁰ O ₂ ⁰ + B ₄ ⁰ O ₄ ⁰ + B ₄ ⁴ O ₄ ⁴ with the parameters B ₂ ⁰ =23659±2 MHz, B ₄ ⁰ =1.9±1 MHz, |B ₄ ⁴ |=54.2±2 MHz, g_‖=1.93±0.02, and g_⊥=1.99±0.02 is used to describe the observed spectra. It is concluded that chromium ions occupy one of the tetrahedrally coordinated cation positions.     

Waves in a superlattice with anisotropic inhomogeneities

Dependences of the dispersion laws and damping of waves in an initially sinusoidal superlattice on inhomogeneities with anisotropic correlation properties are studied for the first time. The period of the superlattice is modulated by the random function described by the anisotropic correlation function K_?(r) that has different correlation radii, k _∥ ^?1 and k _⊥ ^?1 , along the axis of the superlattice z and in the plane xy, respectively. The anisotropy of the correlation is characterized by the parameter λ=1?k_⊥/k_∥ that can change from λ=0 to λ=1 when the correlation wave number k⊥ changes from k_⊥=k_∥ (isotropic 3D inhomogeneities) to k_⊥=0 (1D inhomogeneities). The correlation function of the superlattice K(r) is developed. Its decreasing part goes to the asymptote L that divides the correlation volume into two parts, characterized by finite and infinite correlation radii. The dependences of the width of the gap in the spectrum at the boundary of the Brillouin zone δν and the damping of waves ξ on the value of λ are studied. It is shown that decreasing L leads to the decrease of δν, and increase of ξ, with the increase of λ.     

RETRACTED ARTICLE: Density,viscosity and speed of sound of benzaldehyde with benzene at 303.15, 308.15, and 313.15 K

The values of density, viscosity and speed of sound for the binary liquid mixture of Benzaldehyde with Benzene were measured over the entire range of composition at 303.15, 308.15, and 313.15 K. These values are used to calculate the excess molar volume (V ^E), deviation in viscosity (Δη), deviation in speed of sound (ΔU), deviation in isentropic compressibility (Δβ _s ), excess internal pressure (Δπ), excess intermolecular free length (ΔL _f ), excess free volume (V _E ^f ) and excess acoustic impedance (ΔZ). McAllister’s three-body interaction model is used for correlating Kinematic Viscosity of binary mixtures. The excess values were correlated using the Redlich–Kister polynomial equation to obtain their coefficients and standard deviations. The thermophysical properties (density, viscosity, and speed of sound) under the study were fit to the Jouyban–Acree model.     

<Emphasis Type="Italic">nd</Emphasis> scattering at low energies in the two-body potential model

The S-wave phase shift δ(E) for the spin-doublet nd scattering at low energy E is calculated in the framework of the two-body approach. The effective-range-theory formula k cot δ = (1+k²/k ₀ ² )^?1(?1/α+C₂k²+C₄k⁴) is used to obtain approximate analytical results with different potentials. The corresponding coefficients C₂ and C₄ are obtained from our previous calculations of the asymptotic normalization parameter function C _t ² (aκ), where κ is the triton wave number and a is the doublet nd scattering length. The model reasonably describes δ(E), the results being quite sensitive to the choice of the effective nd potential.     

Novel features of the fragment mass variance in fission of hot nuclei

On the basis of data obtained by the incomplete fusion reactions ⁷Li(43A MeV)+²³²Th and ¹⁴N(34A MeV)+¹⁹⁷Au, the energy dependence of the variance (σ _M ² ) of the fragment mass in fission of highly heated nuclei has been investigated for total excitation energies E _tot ^* ranging from 50 up to 350 MeV. The dependence σ _M ² E _tot ^* shows some unexpected features when E _tot ^* exceeds a value of about 70 MeV. After this value, the steady increase of σ _M ² expected from its temperature dependence changes to some kind of plateau between 100 and 200 MeV. Further on, at E _tot ^* in excess of about 250 MeV, the variance is found to increase again sharply. In order to analyze this behavior quantitatively, a dynamical stochastic model has been developed. The model employs the one-body dissipation mechanism and describes the decay of highly excited and rotating nuclei by fission and light-particle evaporation. It satisfactorily explains the measured prior-to-scission neutron multiplicities and the experimental mass variances up to E _tot ^* ?250 MeV, but the stochastic treatment does not reveal any increase in σ _M ² at higher excitation energies in contradiction with the data.     

Nonergodic state of relaxation ferroelectric Cd<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>7</Subscript> in a constant electric field

The temperature dependence of the residual polarization of the nonergodic relaxation state (NERS) obtained from the measurements of pyroelectric current during zero-field heating (ZFH) in the temperature interval from 10 to 295 K is investigated for the Cd₂Nb₂O₇ relaxation system in two cases: (1) after sample cooling in a constant electric field E (FC) from T = 295 K to a preset temperature, which is much lower than the “freezing” temperature of the relaxation state (T _f ≈ 182 K), field removal, and subsequent cooling in zero field (ZFC) to T = 10 K and (2) after ZFC from T = 295 K to the same temperature below T _f , application of the same field, and FC to T = 10 K. The behavior of the P _r ^FC (T) and P _r ^ZFC (T) dependences is analyzed. In the field E < 2 kV/cm, the P _r ^ZFC curves as functions of 1/T have a broad low-intensity peak in the region T ≈ T _f , which vanishes in stronger fields, when the P _r ^FC (1/T) curves intersect at T ≈ T _f and have no anomalies. The difference in the behavior of P _r ^ZFC (T) and P _r ^FC (T) indicates the difference in the nature of NERS formed during ZFC and FC of the system upon a transition through T _f . In the ZFC mode, NERS exhibits glasslike behavior; in the FC regime, features of the ferroelectric behavior even in the weak field. Analogous variations of P _r ^ZFC (T) and P _r ^FC (T) in a classical ferroelectric KDP are also given for comparison.     

Magnetic properties of Fe<Subscript>3</Subscript>C ferromagnetic nanoparticles encapsulated in carbon nanotubes

The low-temperature dependences of magnetic characteristics (namely, the coercive force H _c , the remanent magnetization M _r , local magnetic anisotropy fields H _a, and the saturation magnetization M _s ) determined from the irreversible and reversible parts of the magnetization curves for Fe₃C ferromagnetic nanoparticles encapsulated in carbon nanotubes are investigated experimentally. The behavior of the temperature dependences of the coercive force H _c (T) and the remanent magnetization M _r (T) indicates a single-domain structure of the particles under study and makes it possible to estimate their blocking temperature T _B = 420–450 K. It is found that the saturation magnetization M _s and the local magnetic anisotropy field H _a vary with temperature as ～T ^5/2.