Substituent Dependent Optical Properties of <Emphasis Type="Italic">p</Emphasis>-phenyl Substituted ethenyl-<Emphasis Type="Italic">E</Emphasis>-thiophenes

Various electron donor and acceptor substituted (NO₂, CN, Cl, H, OCH₃, NH₂) p-phenyl ethenyl-E- thiophenes (1–6) were synthesized and substituent dependent optical properties (dipole moment, transition dipole moment, oscillator strength, optical band gap, hyperpolarizability) were studied using Solvatochromism and Density functional theory. It is shown that thiophene acts as a weak electron donor in presence of an electron withdrawing p-phenyl substituent (NO₂, CN, Cl), whereas thiophene acts as a weak electron acceptor in presence of an electron donating p-phenyl substituent (OCH₃, NH₂). In comparison to ethenyl thiophene 4, the HOMO-LUMO energy band gap is decreased upon increasing the electron donating or electron withdrawing capacity of p-phenyl substituent. From the excited state dipole moment calculation, it is shown that the excited state is highly dipolar for nitro and amino compounds 1 and 6, whereas compounds 2–5 show a non-polar excited state. As compared to the ethenyl thiophene 4, the first hyperpolarizability (β) increases upon substitution either with a strong electron withdrawing or strong electron donating p-phenyl substituent. A large β value is found for p-nitro phenyl ethenyl-E-thiophene and p-amino phenyl ethenyl-E- thiophene. Overall, these studies provide useful information in understanding the optical properties of phenyl and heterocyclic based ethenyl systems.     

New data on the mechanism of decay of the giant dipole resonance in the <Superscript>58</Superscript>Ni nucleus

New data on the mechanism of decay of the giant dipole resonance in the ⁵⁸Ni nucleus are obtained from an analysis of the experimental cross sections for the photonucleon reactions ⁵⁸Ni(γ, p_i)⁵⁷Co and ⁵⁸Ni(γ, n_i)⁵⁷Ni. The method used in this analysis takes into account both the energy spread of the dipole strength concentrated in various isospin components of the giant dipole resonance and the spread of the spectroscopic strength of the populated nucleon-hole states over the levels of the final nuclei. The entire body of experimental spectroscopic information about the levels of the final nuclei ⁵⁷Co and ⁵⁷Ni is employed. It is found that the probability of the semidirect mechanism of decay of the giant dipole resonance in the ⁵⁷Ni nucleus lies in the range 0.16–0.3. The probability of semidirect processes is much higher in the (γ, n) channel (0.28–0.62) than in the (γ, p) channel (0.07–0.17).     

Polarization of phosphorescence transitions and probabilities of intramolecular nonradiative deactivation of the lowest triplet state of aromatic molecules

This study continues the experimental testing of the validity of the inductive resonance theory of dipole-dipole energy transfer from the T ₁→S ₀ transition dipole to stretching vibrations of intramolecular CH bonds of naphthalene and its hydroxy derivatives. To this end, in the series of compounds under study, the range of variation of the geometrical parameter [Φ(CH)]² of the Förster theory, which accounts for the mutual orientation of the energy donor and acceptor, is estimated. Preliminarily, the angles between the transition dipole moments of the radiative and absorptive electronic transitions (T ₁→S ₀ and S ₀→S ₁; T ₁→S ₀ and S ₀→S ₂; S ₁→S ₀ and S ₀ →S ₁; and S ₁→S ₀ and S ₀→S ₂) are measured at 77 K by the method of polarization photoselection. From the polarization measurements, the angles between the phosphorescence transition dipole moment and the plane of a molecule are determined. It was found that, upon passage from naphthalene to its β derivatives, the orientation of the dipole moment of the radiative T ₁→S ₀ transition relative to the plane of a molecule markedly changes, with the in-plane component of the dipole moment being increased by an order of magnitude. The experimentally determined rate constants of nonradiative deactivation of the T ₁ state averaged over the CH groups of the naphthalene ring system, k _nr(CH), are compared with the rate constants [Φ(CH)]² of the inductive resonance energy transfer from the dipole of the T ₁→S ₀ transition to the dipole of the CH vibrations polarized in the plane of a molecule, calculated with regard to the orientational factor [Φ(CH)]². This comparison showed that, in the series of compounds under study, a change in the orientation of the dipole moment of the radiative T ₁→S ₀ transition relative to the plane of a molecule does not affect the rate of the nonradiative T ₁?S ₀ transition. This inference is confirmed by the absence of a correlation between the rate constants k _dd(CH) calculated by us (with regard to [Φ(CH)]²) and the well-known rate constants k _nr(CH) of individual sublevels of the T ₁ state measured at T≤1.35 K for a number of organic molecules. The possible sources of discrepancy between the experimental data that k _nr(CH) is independent of [Φ(CH)]² and the predictions of the theory are considered. A conclusion is made that the electronic-vibrational energy transfer between electric dipoles is the most probable mechanism of the T ₁?S ₀ transitions, but the rate constant of the dipole-dipole energy transfer upon interaction of the electronic and vibrational dipoles in a molecule does not depend on their orientations.     

High-resolution X-ray emission <Emphasis Type="Italic">M</Emphasis>α and <Emphasis Type="Italic">M</Emphasis>β spectra of Bi atoms

The structure and relative intensity of x-ray fluorescence Mα and Mβ spectra of Bi atoms have been studied experimentally under excitation by Cr and Cu Kα_1,2 radiation. It has been found that observed short-wavelength satellites are mostly caused by the radiative transitions M ₅ N-N _6,7 N (M ₅ N satellites) and M ₄ N-N ₆ N (M ₄ N satellites), whereas the transitions M ₅ O-N _6,7 O and M ₄ O-N ₆ O are overlapped with the profiles of x-ray diagram Mα_1,2 and Mβ lines and are not observed as individual structures. The M ₅ N and M ₄ N satellites have been separated from total spectral profiles, and the relative intensities of such groups of lines have been determined. A model has been proposed for calculation of emission cross sections of the M ₄ N and M ₄ N satellites, as well as the Mα_1,2 lines along with the M ₅ O satellites and the Mβ line with the M ₄ O satellites. The model takes into account main channels of generation and migration of vacancies in M subshells connected with the Coster-Kronig transitions M _i -M _j N and M _i -M _j O, radiative transitions M _i -M _j and M _i -N _j , and shaking processes upon production of the M _i vacancy, as well as with cascades of such processes. Comparison of experimental values of the relative intensity of the separated satellites with calculated results indicates the correctness of the model used.     

Analysis of the angular distribution of Auger electrons in a Xe atom

The angular distribution of Auger electrons, and the numerically calculated anisotropy parameters of the angular distribution α for (M₃ → N₂N₃), (M₃ → N₃N₃), (M₄ → N₁N₃), (M₄ → N₄N₅), (M₄ → N₅N₅), and (M_4,5 → O_{2, 3}O_{2, 3}) transitions in a Xe atom are given. The matrix elements are calculated by using the nonrelativistic Hartree-Fock method in LS coupling and the relativistic Hartree-Fock-Dirac method in both jj coupling (the single-configuration approximation) and intermediate coupling (the multiconfiguration approximation).     

On double polarization asymmetries in the elastic electron-proton scattering

Double polarization asymmetry D_p^(M) for the process of elastic electroweak scattering of the longitudinally polarized electrons by polarized proton target is considered with account of anapole G_1p and electric dipole moment (EDM) G_2p proton form factors. This asymmetry is only due to T-parity violating form factor G_2p, but does not directly depend on it, and having a significant value, allows to confirm the existence of the EDM of the proton.     

Auger- und Coster-Kronig-Übergänge der M-Schale von Krypton

The Auger spectra of theM ₂,M ₃,M ₄,M ₅ subshells of krypton and the Coster-Kronig spectra of theM ₁,M ₂,M ₃ subshells of krypton were measured with an electrostatical spectrometer. The ionization in theM shells was caused by electron impact. The use of a gaseous target made it possible to measure the Auger lines even at energies as low as 25 eV. The absolute energies and relative intensities of a great number of transitions were determined: 22 of theM _{4, 5} spectrum, 14 of theM _{2, 3} spectrum and 2 of theM ₁ spectrum. Only in the case of theM _{2, 3} spectrum a comparison between the relative intensities, determined experimentally, and those calculated byRubenstein forZ=47 was possible. The agreement is only qualitatively. Moreover, from the Auger electron energies measured, the following binding energies were calculated:E(M ₁)=(292,1±1,0) eV,E(M ₂)=(222,1±0,6) eV,E(M ₃)=(214,6±0,6)eV,E(N ₁ N ₁)=(62,81±0,05) eV.     

Nondynamical structure of inelastic scattering or reactions of spin type 1+0 → 1+0

The nondynamicalM-matrix formalism is applied to the inelastic scattering or to reactions of spin type 1+0→1+0. It is shown how the parameters of theM-matrix, which contain all dynamical information, can be determined by experiments. There are twoM-matricesM ₊ andM _?, one (M ₊) for the case in which the product of the intrinsic parities of all interacting particles is +1 and one (M _?) where this product is ?1. In the case ofM _? one can avoid triple scattering parameters to determine fully theM _?-matrix.     

<Emphasis Type="Italic">M</Emphasis>α and <Emphasis Type="Italic">M</Emphasis>β X-ray emission spectra of Au atoms upon photoionization of <Emphasis Type="Italic">L</Emphasis> subshells

The structure and relative intensity of the Mα and Mβ X-ray fluorescence spectra of Au atoms are studied experimentally at the energies of absorbed photons both below and above the ionization thresholds of L subshells (Kα_{1, 2} radiation of Cr, Cu, and Mo). The M ₅ N and M ₄ N high-energy satellites are separated from the total spectral profiles and their relative intensities are determined. A model of the M emission is proposed that allows one to take into account the main channels of vacancy transfer from L to M subshells, which are responsible for the generation of double vacancy (M _{4, 5} N and M _{4, 5} O) and triple vacancy (M _{4, 5} N ², M _{4, 5} NO, and M _{4, 5} O ²) states. Comparison of the experimental relative intensities of separated M ₅ N and M ₄ N satellites excited by the Mo Kα_{1, 2} radiation with the calculated results indicates the correctness of the model used. The partial and total M emission cross sections of Au in the absorbed photon energy range of 5–30 keV are calculated. It is found that, in the photon energy region above the ionization threshold of the L ₃ subshell, our results noticeably differ from the data calculated by other authors. Possible reasons for these discrepancies are discussed.     

Effect of gamma radiation on the surface and bulk properties of poly(tetrafluoroethylene)

The effect of gamma radiation on the contact angle θ, the work of adhesion γ _SL for polar and nonpolar liquids, disperse and polar components of the surface energy γ _S , the magnitude of bulk dielectric polarization P ₀, and the dielectric increment Δε for sintered and non-sintered poly(tetrafluoroethylene) (PTFE) of suspension polymerization are studied. Sintered PTFE exhibits anomalously high growth of the studied parameters with an absorbed dose up to 500 kGy: Δε by more than four orders of magnitude, the work of adhesion of the polar liquid \(\gamma _{SL}^{{H_2}O}\) by a factor of 1.5, the polar component of the surface energy γ^pol _S by 20 times. The observed changes are found to be considerably larger than those expected from the viewpoint of the amplification of dipole–dipole and donor–acceptor molecular interactions with the participation of polar groups formed in poly(tetrafluoroethylene) upon irradiation. The similar behavior of Δε, \(\gamma _{SL}^{{H_2}O}\), and γ^pol _S parameters depending on the exposed dose and subsequent annealing of the samples at 150°C is revealed. A unified mechanism for changes in the bulk polarization and surface properties caused by the formation in poly(tetrafluoroethylene) of long-lived electron–hole pairs is suggested.     

Magnetic Properties of Composite Materials Based on a Solid Solution of Type (CuInSe<Subscript>2</Subscript>)<Subscript>1 – <Emphasis Type="Italic">x</Emphasis></Subscript>(MeSe)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> (Me = Mn,Fe) and Polyethylene

Basic magnetic characteristics (coercive force H_c, residual magnetization M_r, magnetization M, and saturation magnetization M_s) of solid solutions of type (CuInSe₂)_1–x(MeSe)_x (Me = Mn, Fe) have been investigated in a wide temperature interval (100–300 K). The existence of a magnetic phase transition has been established for all studied solid solutions at low temperatures, and the Néel temperatures have been determined from the temperature dependences of the magnetization. It is shown that the temperature dependences of coercive force H_c and of magnetization M can be described using the thermal relaxation (fluctuation) theory.     

Electron paramagnetic resonance of Cr<Superscript>3+</Superscript>-Li<Superscript>+</Superscript> centers in (Cr,Li): Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> synthetic forsterite

Synthetic single crystals of chromium-and lithium-doped forsterite, namely, (Cr,Li): Mg₂SiO₄, are studied using electron paramagnetic resonance spectroscopy. It is revealed that, apart from the known centers Cr³⁺(M1) and Cr³⁺(M2) (with local symmetries C_i and C_s, respectively), these crystals involve two new types of centers with C₁ symmetry, namely, Cr³⁺(M1)′ and Cr³⁺(M2)′ centers. The standard parameters D and E in a zero magnetic field [zero-field splitting (ZFS) parameters expressed in GHz] and principal components of the g tensor are determined as follows: D=31.35, E=8.28, and g=(1.9797, 1.9801, 1.9759) for Cr³⁺(M1)′ centers and D=15.171, E=2.283, and g=(1.9747, 1.9769, 1.9710) for Cr³⁺(M2)′ centers. It is found that the lowsymmetric effect of misalignment of the principal axes of the ZFS and g tensors most clearly manifests itself (i.e., its magnitude reaches 19°) in the case of Cr³⁺(M2)′ centers. The structural models Cr³⁺(M1)-Li⁺(M2) and Cr³⁺(M2)-Li⁺(M1) are proposed for the Cr³⁺(M1)′ and Cr³⁺(M2)′ centers, respectively. The concentrations of both centers are determined. It is demonstrated that, upon the formation of Cr³⁺-Li⁺ ion pairs, the M1 position for chromium appears to be two times more preferable than the M2 position. Reasoning from the results obtained, the R₁ line (the ²E → ⁴A₂ transition) observed in the luminescence spectra of (Cr,Li): Mg₂SiO₄ crystals in the vicinity of 699.6 nm is assigned to the Cr³⁺(M1)′ center.     

Quantum-Chemical Simulation of the Solvent Effect on Spontaneous Emission of Singlet Oxygen

A molecular simulation of the solvent effect on radiative rate constant k _r of singlet oxygen is carried out. This study included a search for the most probable conformations of the complexes of molecules of singlet oxygen and ten solvents and calculation of dipole moments M of transitions a¹Δ _g –b¹Σ _g ⁺ (M _a–b ) and a¹Δ _g –X³Σ _g ^- (M _a–X ) of the oxygen molecule for them. Averaging of M _a–b by conformations, taking into account the probability of their formation for complexes without atoms with a large atomic number (Cl, S), yields values that, as a rule, correlate well with the behavior of k _r in the experiment. Taking into account the possibility of decreasing the distance (compared to equilibrium) between molecules in a collision complex at room temperature made it possible to achieve satisfactory agreement of the calculated and experimental data also for complexes with CCl₄, C₂Cl₄, and CS₂. The obtained data indicate that a number of factors affect k _r . The correlation of k _r with molecular polarizability in a number of cases is due, on the one hand, to its effect on the strength of dispersion interactions in the complex and, on the other hand, to the fact that it to some extent reflects the position of the upper filled orbitals of the solvent molecule. Both factors affect the degree of mixing of the π orbitals of the singlet oxygen molecule with the orbitals of the solvent molecule, which, as was found earlier, facilitates the activation of the a¹Δ _g –b¹Σ _g ⁺ transition and the borrowing of its intensity by the a¹Δ _g –X³Σ _g ^- transition.     

Study of Er171 decay by means of an electron-gamma coincidence technique

The decay scheme of Er¹⁷¹ (7.8 h) has been reinvestigated by means of an electron-gamma coincidence spectrometer and a scintillation spectrometer with a transistorized RIDL-400 channel analyser. A careful unfolding of the high energy region of the gamma-ray spectrum revealed the presence of photopeaks at energies of approximately 371, 404, 543, 572, 618, 675, 738, 796, 869, 910 and 962 keV. The existence of 32 transitions in Tm¹⁷¹ was confirmed. Also, it is proved that the 277, 362 keV transitions are in coincidence with the 210 keV and that the 175 keV transition is in coincidence with the 86 keV transition. We revealed the doubt for the existence of the 166, 210, 236, 277 and 419 keV transitions. From coincidence and single counting rates the followingK-conversion coefficients of the 111, 116, 124, 296 and 308 keV transitions were determined to be: α _K (111)=1.561±0.062, α _K (116)=0.699±0.035, α _K (124)=0.608±0.024, α _K (296)=0.0197±0.0010, α _K (308)=0.0183±0.0009, which give the 116, 124 keV transitions an electric quadrupole character; the 111 keV transition a magnetic dipole character withE2/M1 equal 0.4528; and the 296, 308 keV transitions an electric dipole character withM2/E1 equal 0.0058 and 0.0071 respectively.     

Using single donor–acceptor pairs to study the conformational dynamics of macromolecules

It is shown that in the presence of triplet levels of donor and acceptor molecules, the formula for function E(R) describing the dependence of efficiency E of Förster energy transfer on donor–acceptor distance R differs considerably from the one commonly used in experimental works.     

On screening constants in X-ray spectra

Fresh calculations of the X-ray screening constantsσ ₂ forL _II L _III,M _II M _III andM _IV M _V have been made. It has been found thatσ ₂ is not absolutely constant for differentZ. Some regular variations inσ ₂ with electronic shell structure have been noted.     

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.     

Magnetization behavior and metamagnetic transitions in electron-doped manganites induced by a strong magnetic field

The behavior of magnetization M of the R_xA_1?xMnO₃ manganites (R=La, Pr, Nd, Sm, etc., A=Ca, Sr, Ba) in the electron doping region (x<0.4) is studied as a function of external magnetic field H. The M(H) relations for homogeneous magnetic structures are obtained by performing band calculations in the double-exchange model. Three different types of magnetization behavior corresponding to three electron concentration ranges (x<0.14, 0.14<x<0.27, x>0.27) are revealed. The M(H) relations are interpreted in terms of the phase diagram for the homogeneous ground state of the manganites calculated for H=0, and the results agree qualitatively with experimental data on the magnetization of Sm_xCa_1?xMnO₃.     

The vibrational spectrum of the OCS molecule based on the data on spectra of liquid and cryosolutions

The IR absorption spectra of liquid OCS (T = 135(1) K) and of the following solutions—OCS + Ar (T = 90 K), OCS + N₂ (T = 90 K), OCS + Kr (T = 130 K), and OCS + Xe (T = 163 K)—are measured in the range 800–7000 cm^?1. From 16 to 40 bands corresponding to transitions to vibrational states up to the third order inclusive are interpreted for basic isotope modification and for the isotopically substituted molecules ¹⁸O¹²C³²S, ¹⁶O¹³C³²S, and ¹⁶O¹²C³⁴S. In the spectra of the liquids, the spectral moments M(1) and M(2) of all the observed bands are determined. The harmonic frequencies ω _i and the anharmonicity constants x _ik are calculated for all the systems, including the liquid. The anharmonicity is found to be constant within the experimental error. A large shift Δω₃ is primarily determined by the dipole-induced dipole interaction.     

Determination of absoluteK-internal conversion coefficients of some transitions in Ce140 by the internal-external conversion method

The internalK-conversion coefficients of the 331, 431, 815 and 933 keV transitions following the decay of La¹⁴⁰ have been determined absolutely by the method of comparing internal and external conversion lines measured in a double — focusing beta — ray spectrometers. TheK-internal conversion coefficients of the 4+→2+ 487 keV transition in Ce¹⁴⁰ was used to normalize relativeK-electron and gamma-ray intensities for these transitions. The results obtained are:α _K (331)=0.04432±0.00471,α _K (431)=0.28110±0.02913,α _K (815)=0.00396±0.00043,α _K (933)=0.00282±0.00031. Multipolarity assignments based on these values are suggested. The 815 keV transition is found to be pure magnetic dipole character in good agreement with the theoretical values calculated bySliv andBand. The 331 and 933 keV transitions are proved to have magnetic dipole character withE2/M1 equal 0.2852±0.0143 and 0.1750±0.0088 respectively. The 431 keV transition was found to have magnetic octupole character. The results obtained are most consistent with the assignment 2+, 4+, 2+, 3+ and 1+ for the 1597, 2084, 2184, 2410 and 2515 keV levels respectively.