Effect of the structure of a graphite target on the parameters of carbon films obtained by the laser plasma method

We have used Raman light scattering and electron paramagnetic resonance methods to study carbon films obtained by laser plasma deposition, using different types of graphite targets. We have established that the films deposited in this way have a diamond-like structure and are a nanostructured composite containing clusters of both sp² and sp³-hybridized carbon. We have shown that an increase in structural perfection of the graphite target causes an improvement in the structure of the carbon films obtained from it and an increase in the content of sp³-hybridized carbon in it. Thermal stimulation of the substrate during application of a coating leads to the same effect. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 539–546, July–August, 2008.     

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.     

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.     

Interaction of two superhigh-frequency fields with the resonance system of electron spins

Within the framework of the concept of a spin temperature in a steady-state regime, the interaction with a resonance medium of two superhigh-frequency fields, one of which is saturating and the other of which is trial, is considered theoretically in the general case without using a high-temperature approximation. The case where the absorption of a resonance medium vanishes at the trial-field frequency is investigated in detail. This occurs with an intensity of the saturating field lower than in the case of a high-temperature approximation. This intensity is estimated in the second and third orders by the parameter ω₀β_z/2, where ω₀ is the resonance frequency of the transition, β_z=ħ/(kT_z), T_z is the Zeeman-subsystem temperature, ħ is the Planck constant, and k is the Boltzmann constant. It is shown that the cooling of the dipole-dipole reservoir is more considerable than in the case of a high-temperature approximation. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 492–495, July–August, 2000.     

Polarization parameters in systems with spin-spin interactions

The spin-spin interaction of two arbitrary spin systems is considered in some detail. The temporal evolution of the polarization parameters and the correlation parameters has been worked out. Applications of the formalism and the interpretation of the results to processes such as heavy-ion interactions, muon and nuclear repolarization and depolarization in muonic atoms and interactions of multilevel systems are outlined.     

Strong charge carrier effect on the magnetic coupling of La-doped CaMnO3

The exchange interactions in polycrystalline samples of Ca_1−xLa_xMnO₃ (0.00x0.05) are studied by means of Raman scattering and electron paramagnetic resonance. Dramatic reductions in the spin-phonon interactions and magnetic correlations are observed for La doping levels as small as 2–3%. These results show that the charge carriers play an important role in the overall exchange coupling in the electron-doped manganites, even at very low doping levels.     

改变溶液折射率方法研究Fermi共振

Fermi共振现象在光谱分析中的谱线认证、归属有重要应用,然而,它蕴含的丰富物理规律、内容及研究方法亟待开发和研究.本文提出了一种改变溶液折射率研究Fermi共振的方法,该方法以Onsager电介质极化理论为依据,利用分子在溶液中的Raman散射强度(散射系数)随溶液折射率的变化来研究Fermi共振规律.该方法不仅能给出Fermi共振各参数间及与溶液折射率之间的关系,而且发现了Fermi共振双峰的非对称移动、倍频的基频也受Fermi共振调谐等现象.为全面认识Fermi共振规律提供了一种研究方法.     

激光雷达测量大气温度的傅里叶分析方法

在对流层(小于12km）,由于大气中气溶胶的存在,传统的利用大气中瑞利散射光谱测量大气温度的方法具有一定的局限性。借助傅里叶分析方法对不同高度的大气后向散射光谱通过碘吸收池所产生的不同透过率曲线进行处理,同时考虑了对流层中气溶胶的影响,可得到对流层中不同高度、不同大气后向散射比条件下的温度轮廓线。     

Manifestation of the Dynamics of Spin Temperature in EPR in the Absence of Interaction with the Lattice

Within the framework of the concept of spin temperature in electron paramagnetic resonance (EPR) in the absence of the interaction with the lattice, the time dependence for spin temperatures of the Zeeman subsystem and dipole–dipole reservoir is theoretically investigated in both high- and low-temperature approximations. It is shown that the gain can be produced in the system by switching the frequency of the saturating field. The gain in the system as a function of the detuning of the frequency of the saturating field is investigated in a high-temperature approximation. In the presence of a test field in a high-temperature approximation, the possibility of determining the magnitude of a local magnetic field, which is associated with the time of transverse relaxation of the system, is discussed.     

激光雷达测量大气温度的傅里叶分析方法

 在对流层(小于12km），由于大气中气溶胶的存在，传统的利用大气中瑞利散射光谱测量大气温度的方法具有一定的局限性。借助傅里叶分析方法对不同高度的大气后向散射光谱通过碘吸收池所产生的不同透过率曲线进行处理，同时考虑了对流层中气溶胶的影响，可得到对流层中不同高度、不同大气后向散射比条件下的温度轮廓线。     

Double resonance Raman effects in InN nanowires

We study the excitation wavelength dependence of the Raman spectra of InN nanowires. The $ E_1 ({\rm LO})$ phonon mode, which is detected in backscattering configuration because of light entering through lateral faces, exhibits an upward fre‐ quency shift that can be explained by Martin's double resonance. The $ E_1 ({\rm LO})$ /$ E_2^h $ intensity ratio increases with the excitation wavelength more rapidly than the $A_1 ({\rm LO})/E_2^h $ ratio measured in InN thin films. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Theory of phonon-modulated electron spin relaxation time based on the projection reduction method

This paper introduces a new method for a formula for electron spin relaxation time of a system of electrons interacting with phonons through phonon-modulated spin-orbit coupling using the projection-reduction method. The phonon absorption and emission processes as well as the photon absorption and emission processes in all electron transition processes can be explained in an organized manner, and the result can be represented in a diagram that can provide intuition for the quantum dynamics of electrons in a solid. The temperature （T） dependence of electron spin relaxation times （T1） in silicon is T1 ∝ T-1.07 at low temperatures and T1 ∝ T-3.3 at high temperatures for acoustic deformation constant Pad = 1.4 × 10^7 eV and optical deformation constant Pod = 4.0 × 10^17 eV/m. This means that electrons are scattered by the acoustic deformation phonons at low temperatures and optical deformation phonons at high temperatures, respectively. The magnetic field （B） dependence of the relaxation times is T1 ∝ B-2.7 at 100 K and T1 ∝ B-2.3 at 150 K, which nearly agree with the result of Yafet, T1 ∝ B-3.0- B -2.5.     

Study of asymmetric wavenumber shift of the Fermi doublet ν1 − 2ν2 in the Raman spectrum of liquid carbon disulfide

The Raman spectra of liquid carbon disulfide (CS₂) diluted with benzene (C₆H₆) have been measured. By changing the CS₂, the concentration, we found an asymmetric wavenumber shift phenomenon. With decreasing concentration of CS₂, the position of the ν₁ (655 cm⁻¹) band remains practically unchanged, and the 2ν₂ (796 cm⁻¹) band shifts toward higher wavenumbers. To interpret this asymmetric wavenumber shift phenomenon of the Fermi doublet ν₁ − 2ν₂ in the Raman spectra satisfactorily, we propose a modified Bertran model. The values of the Fermi resonance (FR) parameters of CS₂ at different concentrations were calculated using the Bertran equations. In addition, we found the fundamental ν₂, which should be independent of the FR interaction, shifted to higher wavenumbers as the concentration decreased. This shift was probably driven by the tuning of the FR. Copyright © 2009 John Wiley & Sons, Ltd.     

Molecular g-tensors from analytical response theory and quasi-degenerate perturbation theory in the framework of complete active space self-consistent field method

The molecular g-tensor is an important spectroscopic parameter provided by electron para magnetic resonance (EPR) measurement and often needs to be interpreted using computational methods. Here, we present two new implementations based on the first-order and second-order perturbation theories to calculate the g-tensors within the complete-active space self-consistent field (CASSCF) wave function model. In the first-order method, the quasi-degenerate perturbation theory (QDPT) is employed for constructing relativistic CASSCF states perturbed with the spin–orbit coupling operator, which is described effectively in one-electron form with the flexible nuclear screening spin–orbit approximation introduced recently by us. The second-order method is a newly reported approach built upon the linear response theory which accounts for the perturbation with respect to external magnetic field. It is implemented with the coupled–perturbed CASSCF (CP-CASSCF) approach, which provides an equivalent of untruncated sum-over-states expansion. The comparison of the performances between the first-order and second-order methods is shown for various molecules containing light to heavy elements, highlighting their relative strength and weakness. The formulations of QDPT and CP-CASSCF approaches as well as the derivation of the second-order Douglas–Kroll–Hess picture change of Zeeman operators are given in detail.     

Self-compensation characteristics of Eu ions in BaTiO3

In order to clarify whether the mixed valence of Eu²⁺/Eu³⁺ exists in a self-compensation mode in Eu-doped BaTiO₃, the site occupation and valence state of Eu ions in barium titanate were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), electron spin resonance (ESR), Raman spectroscopy (RS), and dielectric measurements. The results indicate that Eu ions may enter both Ba- and Ti-sites as Eu³⁺, forming a self-compensation mode with the amphoteric behavior. Self-compensation characteristics of Eu ions in BaTiO₃ are reflected by an expansion in unit cell volume, evolution of the 830 cm^− 1 Raman band, strong diffusion of the dielectric peak, disappearance of the Eu²⁺ ESR broad signal, and a g = 2.004 signal independent of temperature.     

Visible,near‐infrared,and ultraviolet laser‐excited Raman spectroscopy of the monocytes/macrophages (U937) cells

Raman spectra of the monocytes were recorded with laser excitation at 532, 785, 830, and 244 nm. The measurements of the Raman spectra of monocytes excited with visible, near‐infrared (NIR), and ultraviolet (UV) lasers lad to the following conclusions. (1) The Raman peak pattern of the monocytes can be easily distinguished from those of HeLa and yeast cells; (2) Positions of the Raman peaks of the dried cell are in coincidence with those of the monocytes in a culture cell media. However, the relative intensities of the peaks are changed: the peak centered around 1045 cm⁻¹ is strongly intensified. (3) Raman spectra of the dead monocytes are similar to those of living cells with only one exception: the Raman peak centered around 1004 cm⁻¹ associated with breathing mode of phenylalanine is strongly intensified. The Raman spectra of monocytes excited with 244‐nm UV laser were measured on cells in a cell culture medium. A peak centered at 1485 cm⁻¹ dominates the UV Raman spectra of monocytes. The ratio I₁₅₇₄/I₁₆₁₃ for monocytes is found to be around 0.71. This number reflects the ratio between proteins and DNA content inside a cell and it is found to be twice as high as that of E. coli and 5 times as high as that of gram‐positive bacteria. Copyright © 2009 John Wiley & Sons, Ltd.     

Long and short range spin-spin interactions in ErBaCuO

Dipolar spin-spin interactions play a crucial role as for the magnetic order in the compounds of the RBa₂Cu₃O_6+x family, (R = Dy, Er, Nd). However, inelastic neutron scattering data observed in ErBa₂Cu₃O₇ can be explained only if exchange interactions in addition to dipolar ones are taken into account. Received: 12 January 1998 / Received in final form: 26 March 1998 / Accepted: 10 April 1998     

The resonance and pre‐resonance Raman scattering in the low energy 11B2u and 11B3u states of 1,4,5,8‐naphthalenetetracarboxy dianhydride in terms of DFT methods. The aggregation of NTCDA molecules in the ethanol and methanol solutions

The absorption, pre‐resonance, and resonance Raman spectra of 1,4,5,8‐naphthalenetetracarboxy dianhydride (NTCDA) molecule are examined in terms of time‐dependent density functional theory at TD‐B3LYP/aug‐cc‐pVDZ and TD‐SVWN/aug‐cc‐pVDZ levels. The Franck–Condon analysis performed for two 1¹A_g → 1¹B_2u and 1¹A_g → 1¹B_3u overlapping transitions leads to an excellent agreement between the theoretical predictions and experimental data providing that the calculated absorption is confronted with that measured in chloroform or acetonitrile but not in the ethanol (methanol) solution. We argue that absorption spectra measured in ethanol solution already known in literature do not characterize NTCDA molecule. On the basis of the absorption and resonance scattering spectra, we may deliberate that the dimerization of NTCDA is responsible for utterly different absorption observed in ethanol (methanol) comparing with less active solvents (chloroform and acetonitrile). That conclusion is supported by the dimer vibronic theory and by the TD‐B97d computations at the aug‐cc‐pVDZ basis set level. Copyright © 2013 John Wiley & Sons, Ltd.     

含咔唑与偶氮分散红共聚物的表面增强共振拉曼光谱研究

借助于表面增强共振拉曼光谱散射(SERRS)技术,研究了一种新型的偶氮聚合物材料侧链含咔唑与偶氮分散红共聚物(CAP)在化学沉积法制备的银膜表面的拉曼峰增强和吸附行为。实验结果显示,CAP在银表面的状态为: 聚合物通过咔唑单体中咔唑基团和偶氮单体中硝基与银膜衬底发生物理吸附,而聚合物的主链与衬底相距较远没有相互作用。可以推测,聚合物在衬底表面的这种状态将对偶氮光存储器件的稳定性和工作效率产生不良影响。     

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.