Dipolar excitons in a potential trap in a magnetic field

The conditions for observing the Zeeman spin splitting compensation in an exciton Bose gas have been investigated. The magnetoluminescence of spatially indirect, dipolar excitons in a 25-nm-wide GaAs/AlGaAs quantum well upon their accumulation in a lateral electrostatic trap has been studied in the Faraday geometry. The critical magnetic field B _cr below which the spin (paramagnetic) splitting of the luminescence line for a heavy-hole exciton at the trap center is almost completely compensated due to the exchange interaction in a dense Bose gas has been found to increase linearly with exciton concentration in qualitative agreement with the theory. Using a potential trap is fundamentally important. Incomplete compensation is observed in a homogeneous photoexcitation spot for dipolar excitons: the splitting is considerably smaller than that for a spatially direct exciton but differs noticeably from zero. The spin splitting compensation effect is observed only under neutral charge balance conditions—there is no Zeeman splitting suppression in a charged quantum well.     

Calculation of the rate constants of spin exchange between paramagnetic particles with arbitrary spins for their diffusion motion in nonviscous liquids

The rate constant of spin exchange between two paramagnetic particles with arbitrary spins is calculated within a model of diffusion passage through a region of exchange interaction that exponentially depends on the interparticle distance.     

An electron spin resonance study of proton transfer equilibria involving the semiquinone radicals derived from hydroquinone and catechol

The electron spin resonance spectra of the semiquinone radicals derived from hydroquinone and catechol have been studied in aqueous solutions of varying ph in a rapid flow system. The spectra were found to change drastically with ph; these effects are attributed to protonation of the semiquinones at rates which are dependent on the ph. Models for the systems are proposed, and the effects of exchange are described by means of the modified Bloch equations. Estimates are made of the rate constants and equilibrium constants for protonation of the semiquinone radicals and limits are set for the rate of hydroxyl proton exchange between the radical species and solvent in the low ph region.     

Structure functions and ionization of isolated atoms by charged projectiles

Inner-shell ionization of isolated atoms by incident charged particles is reexamined in the one-photon-exchange approximation. Within this framework we advocate the use of structure functions, which is popular in nuclear and particle physics. This method allows to obtain compact Lorentz- and gauge-invariant expressions. Projectiles of any spin and internal structure are easily accomodated in the formalism.K-shell ionization by relativistic electrons is calculated in a simple model.     

The Structure and EPR Behavior of Short Nitroxide Biradicals Containing Sulfur Atom in the Bridge

Two short nitroxide biradicals of similar composition: S(OR₆)₂ (1) and O=S(OR₆)₂ (2), where OR₆ is 1-oxyl-2,2,6,6-tetramethyl-4-oxypiperidine, have been studied by electron paramagnetic resonance spectroscopy, and X-ray structural analysis. Variations of the intramolecular electron spin exchange in the biradicals, dissolved in toluene and ethanol, as a function of temperature were characterized by changes in the isotropic ¹⁴N hyperfine splitting constant a, values of the exchange integral $ \left| J \right|, $ and compared with the X-ray structural data. Thermodynamic parameters of the conformational rearrangements were calculated. Geometry optimization and spin density distribution calculations of biradicals 1 and 2 were carried out on the DFT/UB3LYP/cc-pVdz and DFT/ROPBE/N07D levels of theory. Structural rigidity and probable differences in biradicals behavior are discussed.     

Monte Carlo study of small magnetic particles

In earlier computer simulation small magnetic particles with nearest neighbor Heisenberg interactions in zero magnetic field have been studied. We now continue these investigations including next nearest neighbor exchange and non zero magnetic fieldsH. The particles treated have spherical shape with a number of spinsN in the range from 33 to 3071. It is shown that the spontaneous magnetization of the particles is rather different from the bulk magnetization. The magnetization process can be accounted for by the Néel theory, if the correct spontaneous magnetization of the particle is used. The distribution of local magnetizations (the magnetic “profile”) was also obtained in various cases. It is shown that the magnetization of very small particles is much more depressed than predicted by the mean field approximation. We introduce an “effective magnetic radius” \(\hat R\) accounting for the reduction of the local magnetization. This magnetic radius is important for the interpretation of experimental results. A distinct dependence of \(\hat R\) on the magnetic field, temperature and the fraction of next nearest neighbor exchange is found. Finally a brief comparison is made with the recent study of magnetic surface properties by Binder and Hohenberg.     

Pair Production and Solutions of Wave Equation for Arbitrary-Spin Particles

We investigate the theory of particles with arbitrary spin and magnetic moment in the Lorentz representation (0, s) (s, 0) in an external constant and uniform electromagnetic field. We obtain the density matrix of free particles in pure spin states. The differential probability of pair producing particles with arbitrary spin by an external constant and uniform electromagnetic field is found using the exact solutions. We calculate the imaginary and real parts of the Lagrangian in an electromagnetic field that takes into account the vacuum polarization.     

Exact cosmological solution with particle creation in JBD theory

Exact solutions are sought by taking the generated particles of spin 1/2 (according to the creation rate of Schäfer and Dehnen [1]) as matter sources of the Cosmological equations of JBD theory. There exists one exact solution for which the gravitational constant decreases linearly with time and the mass of the universe increases proportionally to the square of its age (Dirac's hypotheses). The radius of curvature increases linearly with time while the density decreases inversely with it. It is found that for an age of the universe 10^–22 sec only two particles have populated the universe. This is assumed to be the initial state of the model. The calculated present particle number and their density are in agreement with the observed data. This model implies that all present matter (excluding the two initial particles) has been created by the expansion of the universe.Supported in part by CONACYT grant No. 11358.     

Spin flip due to the spin–orbit interaction of colliding slow charged particles

The scattering amplitudes of point charged particles is calculated analytically taking into account the spin–orbit interaction. We have considered two cases typical of a hydrogen-like plasma: scattering of an electron by a heavy ion and scattering of an electron by a free electron. The results have been obtained taking into account the ranges of low collision energies smaller than α² m _e c ², where α is the fine structure constant.     

Determination of the deuterium content of deuterated betaine arsenate by electron spin echo envelope modulation

An alternative method for the determination of the deuterium content in the hydrogen bonds of ferroelectric/antiferroelectric deuterated betaine arsenate is presented. Carbon radicals formed by gamma irradiation of the betaine arsenate have been used as paramagnetic probes. The deuterium content in the hydrogen bonds has been determined by analyzing the modulation in the electron spin echo spectra of the carbon radical (CH₃)₃N+CHCOO^? which arises because of the dipolar interactions between the paramagnetic radical and the deuterium nuclei.     

范德瓦耳斯分子K39Xe129中的自旋-转动对自旋交换耦合常数之比的确定

光泵的方法被用来确定K³⁹Xe¹²⁹范德瓦耳斯分子中的自旋-转动耦合常数对自旋交换耦合常数的比值X。详细地讨论了这些测量理论。得到比值X=γN/α=4.8(1)。 关键词：     

Relaxation of protons by radicals in rotationally immobilized proteins

Proton spin-lattice relaxation by paramagnetic centers may be dramatically enhanced if the paramagnetic center is rotationally immobilized in the magnetic field. The details of the relaxation mechanism are different from those appropriate to solutions of paramagnetic relaxation agents. We report here large enhancements in the proton spin-lattice relaxation rate constants associated with organic radicals when the radical system is rigidly connected with a rotationally immobilized macromolecular matrix such as a dry protein or a cross-linked protein gel. The paramagnetic contribution to the protein-proton population is direct and distributed internally among the protein protons by efficient spin diffusion. In the case of a cross-linked-protein gel, the paramagnetic effects are carried to the water spins indirectly by chemical exchange mechanisms involving water molecule exchange with rare long-lived water molecule binding sites on the immobilized protein and proton exchange. The dramatic increase in the efficiency of spin relaxation by organic radicals compared with metal systems at low magnetic field strengths results because the electron relaxation time of the radical is orders of magnitude larger than that for metal systems. This gain in relaxation efficiency provides completely new opportunities for the design of spin-lattice relaxation based contrast agents in magnetic imaging and also provides new ways to examine intramolecular protein dynamics.     

Time-resolved EPR study of electron spin polarization and spin exchange in mixed solutions of porphyrin stable free radicals

The time-resolved electron paramagnetic resonance (EPR) spectra are studied in the temperature range of 110–300 K for two mixed solutions of porphyrins, ZnTPP and H₂TPP, in toluene and the stable free radical 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO). The EPR spectra and their kinetic behavior were studied for concentrations of TEMPO varied in the interval from 0.51 to 7.68 mM, while the porphyrin concentration was fixed as 1 mM. The EPR spectra of triplet-state porphyrins and free radicals manifest the chemically induced spin polarization. For the relatively short-lived radical-triplet pairs, with the perturbation theory up to the fourth order, the theoretical expressions are obtained for the triplet and radical spin polarization induced by the enhanced intersystem crossing (ISC) due to the interaction of excited singlet-state porphyrins with free radicals and by the triplet quenching by free radicals. The time-dependent EPR spectra of the triplets are simulated taking into account the spin-lattice relaxation. It is shown that the variation of the triplet EPR spectra shape, when the time of observation increases, arises from the spin-lattice relaxation kinetics. The kinetic behavior of the TEMPO EPR spectrum was simulated on the basis of the kinetic scheme suggested earlier in the literature. The triplet spin-lattice relaxation time, the rate of the ISC and the lifetime of the excited singlet state were estimated by fitting the kinetic curves for the triplet EPR spectra intensity. For the mixed porphyrin-TEMPO solutions, a possible set of the rate constants of important bimolecular processes were determined. For this set of parameters, it turns out that the spin polarization transfer has a smaller rate constant than the rate constant of the diffusion collisions of the triplet and radical. It appears that the rate constant of the ISC catalyzed by radicals is relatively high in the solutions close to the melting point of the solvent and in the soft-glassy state. In the triplet porphyrins the initial spin polarization induced by the spin-selective ISC was found to exceed the equilibrium spin polarization by up to two orders of magnitude.     

Paramagnetic Proton Nuclear Spin Relaxation Theory of Low-Symmetry Complexes for Electron Spin Quantum NumberS=

A generalization of the modified Solomon–Bloembergen–Morgan (MSBM) equations has been derived in order to describe paramagnetic relaxation enhancement (PRE) of paramagnetic complexes characterized by both a transient (Δ^ZFS_t) and a static (Δ^ZFS_s) zero-field splitting (ZFS) interaction. The new theory includes the effects of static ZFS, hyperfine coupling, and angular dependence and is presented for the case of electron spin quantum numberS= , for example, Mn(II) and Fe(III) complexes. The model gives the difference from MSBM theory in terms of a correction term δ which is given in closed analytical form. The theory may be important in analyzing the PRE of proton spin–lattice relaxation dispersion measurements (NMRD profiles) of low-symmetry aqua–metal complexes which are likely to be formed upon transition metal ions associated with charged molecular surfaces of biomacromolecules. The theory has been implemented with a computer program which calculates solvent water protonT₁NMRD profiles using both MSBM and the new theory.     

A CW-EPR and ESEEM spectroscopic study of the dithiadiazolyl radicals p-XC6F4CNSSN (X = CN, Br)

Two dithiadiazolyl radicals, p-NCC₆F₄CNSSN and p-BrC₆F₄CNSSN, have recently been found to be paramagnetic in the solid state. While the β-phase of the first one exhibits spontaneous magnetization below 36 K, the second one shows a paramagnetic character in the solid state. The spin density distribution in these radicals is examined through continuous-wave electron paramagnetic resonance and electron spin echo envelope modulation spectroscopies. Hyperfine correlation sublevel spectroscopy provides information about the interaction of the unpaired spin with F and N nuclei. A signal coming from the interaction with Br nucleus is also detected. The superhyperfme coupling constants of the unpaired electron with the magnetic nuclei are obtained and values of the corresponding spin densities, ?_s and ?_σ - ?_π, can be estimated in the isolated radicals. Spin density distribution has also been calculated in both molecules with density functional theory, being in excellent agreement with those determined from the spectra. The spin density is mainly concentrated in the dithiadiazolyl ring, but some spin density is observed on the fluorinated aromatic rings. They also provide a strong basis to understand the differences of the magnetic behavior of both molecules in terms of their respective packing in the solid state.     

A paramagnetic molecular voltmeter

We have developed a general electron paramagnetic resonance (EPR) method to measure electrostatic potential at spin labels on proteins to millivolt accuracy. Electrostatic potential is fundamental to energy-transducing proteins like myosin, because molecular energy storage and retrieval is primarily electrostatic. Quantitative analysis of protein electrostatics demands a site-specific spectroscopic method sensitive to millivolt changes. Previous electrostatic potential studies on macromolecules fell short in sensitivity, accuracy and/or specificity. Our approach uses fast-relaxing charged and neutral paramagnetic relaxation agents (PRAs) to increase nitroxide spin label relaxation rate solely through collisional spin exchange. These PRAs were calibrated in experiments on small nitroxides of known structure and charge to account for differences in their relaxation efficiency. Nitroxide longitudinal (R(1)) and transverse (R(2)) relaxation rates were separated by applying lineshape analysis to progressive saturation spectra. The ratio of measured R(1) increases for each pair of charged and neutral PRAs measures the shift in local PRA concentration due to electrostatic potential. Voltage at the spin label is then calculated using the Boltzmann equation. Measured voltages for two small charged nitroxides agree with Debye-Hückel calculations. Voltage for spin-labeled myosin fragment S1 also agrees with calculation based on the pK shift of the reacted cysteine.     

Tailored Nitroxide Radicals and Biradical Containing <Superscript>13</Superscript>C Enriched Acetylene Groups: ENDOR and DFT Investigation

A specially synthesized nitroxide biradical R₅-C≡¹³C-(p-C₆H₄)₂-¹³C≡C-R₅ (B4) and two radicals, R₅-C≡¹³CH (RCC) and R₅-C≡¹³C-C₆H₅ (RCCPh), where R₅ is 1-oxyl-2,2,5,5-tetramethyl-pyrroline group, have been studied by X- and W-band electron paramagnetic resonance (EPR) spectroscopy, and by W-band electron-nuclear double resonance (ENDOR). Spin density distribution and hyperfine splitting (hfs) constants on ¹³C atoms were experimentally determined and also calculated using ORCA 3.0.3 program package. The biradical and radicals geometries were optimized on UKS/B3LYP/cc-pVDZ level. Hfs constants were calculated using density functional theory (DFT) with PBE0 functional and N07D, and were compared with the experimental value of the hfs constant on ¹³C atoms, measured from ENDOR spectra. It is concluded that at small values of the exchange integral as J ≤ a/2 ≈ 7–8 G, the current quantum chemical approaches do not allow determining precise values of the hfs constants on the ¹³C atoms in the bridge connecting two paramagnetic nitroxide rings of the biradical.     

Bipolar charging of dust particles under ultraviolet radiation

The photoemission charging of dust particles under ultraviolet radiation from a xenon lamp has been investigated. The velocities of yttrium dust particles with a work function of 3.3 eV and their charges have been determined experimentally; the latter are about 400–500 and about 100 elementary charges per micron of radius for the positively and negatively charged fractions, respectively. The dust particle charging and the dust cloud evolution in a photoemission cell after exposure to an ultraviolet radiation source under the applied voltage have been simulated numerically. The photoemission charging of dust particles has been calculated on the basis of nonlocal and local charging models. Only unipolar particle charging is shown to take place in a system of polydisperse dust particles with the same photoemission efficiency. It has been established that bipolar charging is possible in the case of monodisperse particles with different quantum efficiencies. Polydispersity in this case facilitates the appearance of oppositely charged particles in a photoemission plasma.     

Spin relaxation measurements of electrostatic bias in intermolecular exploration

We utilize the paramagnetic contribution to proton spin-lattice relaxation rate constants induced by freely diffusing charged paramagnetic centers to investigate the effect of charge on the intermolecular exploration of a protein by the small molecule. The proton NMR spectrum provided 255 resolved resonances that report how the explorer molecule local concentration varies with position on the surface. The measurements integrate over local dielectric constant variations, and, in principle, provide an experimental characterization of the surface free energy sampling biases introduced by the charge distribution on the protein. The experimental results for ribonuclease A obtained using positive, neutral, and negatively charged small nitroxide radicals are qualitatively similar to those expected from electrostatic calculations. However, while systematic electrostatic trends are apparent, the three different combinations of the data sets do not yield internally consistent values for the electrostatic contribution to the intermolecular free energy. We attribute this failure to the weakness of the electrostatic sampling bias for charged nitroxides in water and local variations in effective translational diffusion constant at the water-protein interface, which enters the nuclear spin relaxation equations for the nitroxide-proton dipolar coupling.