Effect of oxygen diffusion on the relaxation parameters of paramagnetic centers on the surface of alumina

The present article is concerned with theoretical consideration of the effect of oxygen diffusion on the relaxation parameters of paramagnetic centers (PC) located on a surface. Proceeding from a model of dipole-dipole interaction between paramagnetic molecules of O₂ and PC that is modulated by translational diffusion motion of O₂ molecules in the volume and on surface of an adsorbent and in its pores, we give an explanation for the observed dependence of the intensity of the EPR signal on the pressure of O₂. In the present case, diffusion in the volume is the decisive factor. We also managed to explain the presence of an SHF field power threshold for the indicated phenomenon to be observed. In the calculations we used correlation functions obtained earlier for diffusion in a volume. Institute of Physicoorganic Chemistry, National Academy of Sciences of Belarus, 13, Surganov St., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 2, pp. 230–235, March–April, 1998.     

Dynamic polarization of a nuclear zeeman subsystem within the framework of the EPR spin-temperature concept

In a high-temperature approximation, theoretical consideration is given to dynamic polarization of nuclei within the framework of the EPR spin-temperature concept. We show that the maximum polarization of nuclei can be attained at a certain value of the detuning of an SHF-field if the intensity of the latter is fixed. The possibility of determining some relaxation parameters of the system by the value of this detuning at a high value of the saturating field is shown. In the presence of a trial field, the effect of a nuclear Zeeman subsystem on the time of transverse relaxation T₂ is evaluated. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 3, pp. 404–406, May–June, 2000.     

Investigation of the possibilities of measuring relaxation parameters by the EPR method within the framework of the concept of spin temperature

Procedures for measuring some relaxation parameters of uniformly and nonuniformly broadened systems by the EPR method in a high-temperature approximation are proposed. The theoretical consideration is based on the concept of spin temperature and Provotorov's equations. A trial field is used along with a saturating superhigh-frequency field. The measuring methods for the time of the transverse relaxation T₂ in the case of uniform broadening and some relaxation parameters or their combinations in the case of nonuniform broadening are based on measuring the frequency characteristics of the system when the absorption becomes zero at the frequency of the trial field. Institute of Physical and Organic Chemistry, National Academy of Sciences of Belarus, 13, Surganov Str., Minsk, 220072. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 266–270, March–April, 1999.     

Dynamics of Spin Temperatures in EPR on Rapid Switching of the Frequency Detuning of a Saturating Field

In the framework of the spin temperature in EPR in the absence of interaction with the lattice, the time-dependent change in the spin temperatures of the Zeeman subsystem and dipole-dipole reservoir has been investigated theoretically in the high-temperature approximation. It is shown that amplification in the system can be obtained by switching the detuning of the saturating field frequency. The approach to the solution of the problem is based on the fact that during the process of switching and establishment of both temperatures the total energy of the Zeeman subsystem and of the dipole-dipole reservoir is preserved. It has been established that the values of absorption or amplification in the system depend on the frequency detunings of the saturating field. In the presence of a probe field, the possibility of determining the value of the local magnetic field related to the time of transverse relaxation of the system is demonstrated.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 171–175, March–April, 2005.     

Determination of T1-spin-lattice relaxation time in a two-level system by continuous wave multiquantum electron paramagnetic resonance spectroscopy in a presence of tetrachromatic microwave irradiation

Applicability of continuous wave multiquantum EPR methods to study relaxation times at X-band is examined. Multiquantum transitions excited in a two-level system by tetrachromatic irradiation are used for these studies. The Bloch equation model is applied to simulate lineshapes of the three quantum transitions as a function of frequency difference between exciting fields. The dependence of multiquantum transition signals on relaxation times and microwave amplitude is shown. On this basis a method of deducing relaxation times from these signals is formulated. The case of a homogeneously and inhomogeneously broadened resonance line is considered. Two experimental methods are used to verify the proposed hypothesis: the X-band continuous wave multiquantum EPR with four frequencies microwave field and saturation recovery EPR. The values of T₁ obtained from CW MQ EPR and SR EPR are compared.     

Relaxation of Paramagnetic Centers during Modulation of a Stationary Magnetic Field

It has been found that the phase shift _min in the synchronous detection block that ensures the minimum amplitude of the EPR lines of ruby, diphenylpicrylhydrazyl, and MnSO₄·5H₂O, depends on the amplitude of the modulationH _m of a stationary magnetic field. The dependence of _min on H _m is explained by the inertial nature of the recovery of the stationary states of paramagnetic centers on a change in the magnetic field strength.     

A novel approach to the simulation of nitroxide spin label EPR spectra from a single truncated dynamical trajectory

A simple effective method for calculation of EPR spectra from a single truncated dynamical trajectory of spin probe orientations is reported. It is shown that an accurate simulation can be achieved from the small initial fraction of a dynamical trajectory until the point when the autocorrelation function of re-orientational motion of spin label has relaxed. This substantially reduces the amount of time for spectra simulation compared to previous approaches, which require multiple full length trajectories (normally of several microseconds) to achieve the desired resolution of EPR spectra. Our method is applicable to trajectories generated from both Brownian dynamics and molecular dynamics (MD) calculations. Simulations of EPR spectra from Brownian dynamical trajectories under a variety of motional conditions including bi-modal dynamics with different hopping rates between the modes are compared to those performed by conventional method. Since the relatively short timescales of spin label motions are realistically accessible by modern MD computational methods, our approach, for the first time, opens the prospect of the simulation of EPR spectra entirely from MD trajectories of real proteins structures.     

Probing the paramagnetic interactions between the unpaired electronic spins of carbon atoms and the nuclear spins of hydrogen molecules with Raman spectroscopy

Carbon materials typically have a high density of unpaired electronic spins but the exact nature of the defect sites that give rise to their magnetic properties are not yet well understood. In this work, the paramagnetic interactions between the unpaired electronic spins of carbon atoms and the nuclear spins of hydrogen molecules were probed with Raman spectroscopy by monitoring the relative population of H₂ rotational states. For H₂, the symmetries of nuclear spin and rotational wave functions are correlated. Because of the weak interactions between H₂ nuclear spins, the transitions between odd and even rotational states are normally hindered. The magnetic field generated by unpaired electronic spins relaxes the selection rules and promotes transitions between H₂ rotational levels of different symmetry. This affects the rotational levels' relaxation kinetics toward equilibrium and makes H₂ molecules useful to study unpaired electrons in paramagnetic materials. It is suggested that simultaneous electron paramagnetic resonance and Raman measurements on carbon materials interacting with hydrogen molecules could result in a better understanding of the nature of paramagnetic defects in carbon materials, which could have a substantial impact on Li‐ion batteries or for understanding the graphene electronic properties. Copyright © 2011 John Wiley & Sons, Ltd.     

Temperature dependence of rotational relaxation of methane in the 2ν3 vibrational state by self- and nitrogen-collisions and comparison with line broadening measurements

Depopulation rates of rotational levels in the v₃ = 2 vibrational state of ¹²CH₄ are investigated by a pump-probe technique. Methane molecules are excited into selected rotational levels by tuning the pump laser to 2ν₃ lines. The time evolution in population of the excited level after the pumping pulse is monitored by tuning the probe laser to a (3ν₃ ← 2ν₃) line corresponding to a transition with the excited rotational level as the lower level. Measurements were performed from room temperature down to 100 K in pure CH₄ and in CH₄-N₂ mixtures. The rotational relaxation rate coefficients are given for the J = 1, A₂, J = 1, E, J = 1, F₂ and J = 0, F₂ levels. The results are compared with the available data on line broadening coefficients. The temperature dependence of the data on N₂-broadening is particularly well reproduced by the power law deduced from the results on rotational relaxation.     

Upper bound for the time derivative of entropy for a stochastic dynamical system with double singularities driven by non-Gaussian noise

A stochastic dynamical system with double singularities driven by non-Gaussian noise is investigated. The Fokker--Plank equation of the system is obtained through the path-integral approach and the method of transformation. Based on the definition of Shannon's information entropy and the Schwartz inequality principle, the upper bound for the time derivative of entropy is calculated both in the absence and in the presence of non-equilibrium constraint. The present calculations can be used to interpret the effects of the system dissipative parameter, the system singularity strength parameter, the noise correlation time and the noise deviation parameter on the upper bound.     

Surface chemistry and catalysis of oxide model catalysts from single crystals to nanocrystals

Fundamental understandings of surface chemistry and catalysis of solid catalysts are of great importance for the developments of efficient catalysts and corresponding catalytic processes, but have been remaining as a challenge due to the complex nature of heterogeneous catalysis. Model catalysts approach based on catalytic materials with uniform and well-defined surface structures is an effective strategy. Single crystals-based model catalysts have been successfully used for surface chemistry studies of solid catalysts, but encounter the so-called “materials gap” and “pressure gap” when applied for catalysis studies of solid catalysts. Recently catalytic nanocrystals with uniform and well-defined surface structures have emerged as a novel type of model catalysts whose surface chemistry and catalysis can be studied under the same operational reaction condition as working powder catalysts, and they are recognized as a novel type of model catalysts that can bridge the “materials gap” and “pressure gap” between single crystals-based model catalysts and powder catalysts. Herein we review recent progress of surface chemistry and catalysis of important oxide catalysts including CeO₂, TiO₂ and Cu₂O acquired by model catalysts from single crystals to nanocrystals with an aim at summarizing the commonalities and discussing the differences among model catalysts with complexities at different levels. Firstly, the complex nature of surface chemistry and catalysis of solid catalysts is briefly introduced. In the following sections, the model catalysts approach is described and surface chemistry and catalysis of CeO₂, TiO₂ and Cu₂O single crystal and nanocrystal model catalysts are reviewed. Finally, concluding remarks and future prospects are given on a comprehensive approach of model catalysts from single crystals to nanocrystals for the investigations of surface chemistry and catalysis of powder catalysts approaching the working conditions as closely as possible.