Vibrational and orientational relaxation of thiocyanate ion in crown ether complexes

The IR absorption and Raman spectra of the following complex compounds based on thiocyanates and crown ethers have been studied: KSCN-18-crown-6, KSCN-dibenzo-18-crown-6, NaSCN-dibenzo-18-crown-6, and NaSCN-benzo-15-crown-5. The shape of the contour of the spectral line corresponding to the stretching vibration ₁(CN) of the thiocyanate ion in the indicated compounds in the temperature interval involving solid and liquid phases have been investigated for the first time. The reorientation parameters and molecular-relaxation characteristics of the thiocyanate ion in the crown compounds have been calculated. It is found that an increase in temperature leads to gradual freeing of cations and to the properties of crown compounds becoming identical to those of pure salt melts.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 23–27, January–February, 2005.     

Measurement of strong interaction parameters in antiprotonic hydrogen and deuterium

In the PS207 experiment at CERN, X-rays from antiprotonic hydrogen and deuterium have been measured at low pressure. The strong interaction shift and the broadening of the K _α transition in antiprotonic hydrogen were determined. Evidence was found for the individual hyperfine components of the protonium ground state. This revised version was published online in August 2006 with corrections to the Cover Date.     

Anomalous temperature dependence of resistivity in quasi-one-dimensional conductors in a strong magnetic field

We present a heuristic, semiphenomenological model of the anomalous temperature (T) dependence of resistivity recently observed experimentally in the quasi-one-dimensional (Q1D) organic conductors of the family in moderately strong magnetic fields. We suggest that a Q1D conductor behaves like an insulator (), when its effective dimensionality is one, and like a metal (), when its effective dimensionality is greater than one. Applying a magnetic field reduces the effective dimensionality of the system and switches the temperature dependence of resistivity between the insulating and metallic laws depending on the magnitude and orientation of the magnetic field. We critically analyze whether various microscopic models suggested in literature can produce such a behavior and find that none of the models is fully satisfactory. In particular, we perform detailed analytical and numerical calculations within the scenario of magnetic-field-induced spin-density-wave precursor effect suggested by Gor'kov and find that the theoretical results do not agree with the experimental observations. Received 20 October 1998     

Solution dynamics of the natural bioactive molecule capsaicin: a relaxation study

Nuclear magnetic resonance spectroscopy is a straightforward technique for studying molecular dynamics that range in timescale from picosecond (motions faster than molecular reorientation) to those that occur in real-time. This approach is important to highlight the behavior of bioactive molecules in solution, and to acquire information about action mechanisms and potential pharmacological effects. Proton and carbon-13 spin–lattice relaxation experiments were performed to calculate the reorientational correlation time for protonated carbons. Capsaicin showed complex dynamical properties and the results revealed two regions with different dynamical properties: the aliphatic region with fast reorientation motions and the aromatic region with slow motions.     

Simple one-dimensional interaction systems with superexponential relaxation times

Finite one-dimensional random processes with local interaction are presented which keep some information of a topological nature about their initial conditions during time, the logarithm of whose expectation grows asymptotically at least asM ³, whereM is the size of the setR _M of states of one component. ActuallyR _M is a circle of lengthM. At every moment of the discrete time every component turns into some kind of average of its neighbors, after which it makes a random step along this circle. All these steps are mutually independent and identically distributed. In the present version the absolute values of the steps never exceed a constant. The processes are uniform in space, time, and the set of states. This estimation contributes to our awareness of what kind of stable behavior one can expect from one-dimensional random processes with local interaction.Partially supported by NSF grant #DMS-932 1216.     

Origin of the fast magnetization relaxation at low temperatures in HTS with strong pinning

The temperature T variation of the normalized magnetization relaxation rate S in high-temperature superconductors (HTS) with strong vortex pinning exhibits a maximum in the low-T range. This was reported for various HTS, and the origin of the faster relaxation at low T appearing in standard magnetization relaxation measurements was usually related to specific pinning properties of the investigated specimens. Since the observed behaviour seems to be characteristic to all HTS with enhanced pinning (generated by random and/or correlated disorder), we show that the S(T) maximum can be explained in terms of classic collective vortex creep. The influence of thermo-magnetic instabilities in the low-T range is also evidenced. The collective (elastic) creep regime is generated by the T dependent macroscopic currents induced in the sample during standard magnetization measurements.     

Nonmonotonic temperature dependence of the Hall resistance of a 2D electron system in silicon

For a 2D electron system in silicon, the temperature dependence of the Hall resistance ρ_xy(T) is measured in a weak magnetic field in the range of temperatures (1–35 K) and carrier concentrations n where the diagonal resistance component exhibits a metallic-type behavior. The temperature dependences ρ_xy(T) obtained for different n values are nonmonotonic and have a maximum at T_max ～ 0.16T_F. At lower temperatures T < T_max, the change δρ_xy(T) in the Hall resistance noticeably exceeds the interaction quantum correction and qualitatively agrees with the semiclassical model, where only the broadening of the Fermi distribution is taken into account. At higher temperatures T > T_max, the dependence ρ_xy(T) can be qualitatively explained by both the temperature dependence of the scattering time and the thermal activation of carriers from the band of localized states.     

Vibrational relaxation study in carbonyl containing molecule: role of hydrodynamic and dispersion forces

The isotropic Raman component of the C = O stretching mode of ethyl acetate (EA) was analyzed using various polar and nonpolar solvents. It was found that the bandshape approaches towards Lorentzian at high dilution using the curve‐fitting method. The isotropic Raman band was also analyzed by estimating the correlation coefficient with reference to the Lorentzian lineshape using a simple method of linear‐curve fitting. The effects of dispersion and hydrodynamic forces on bandwidth were studied in details. The vibrational relaxation rate was studied using certain parameters and it was found that the microscopic based parameter can explain the complexities occurring in solute–solvent interactions. Copyright © 2007 John Wiley & Sons, Ltd.     

Influence of interface interaction on enthalpy relaxation in polysiloxane-modified epoxy resin

The enthalpy relaxation and dynamic relaxation properties of phenol-formaldehyde novolac-cured o-cresol novolac epoxy resin modified with hydroxyl-terminated polysiloxane were studied by differential scanning calorimeter (DSC) and torsional pendulum analysis. The results show that the extent and rate of enthalpy relaxation are closely related to the amount of modifier and the ratio of modifier and coupling agent: the (β′ relaxation that appeared at around 40°C in the dynamic relaxation spectra is found to be correlated with the interfacial stress at the interface between the epoxy resin matrix and polysiloxane domain.     

硝基甲烷振动能量弛豫的集体模型

用分子动力学方法结合Dlott等人提出的"门槛模"理论研究集体相互作用下硝基甲烷振动能量弛豫过程.其中振动冷却过程与实验符合的很好.在振动激发过程的分子动力学模拟中观测到与实验一致的基频频移现象.用分子动力学方法从微观上详细地描述出分子"门槛模"振动激发过程.研究表明,在高温高压作用下,集体作用效应对多原子振动激发具有不可忽视的作用,能量传递过程中除了基频的作用外,强烈的非线性相互作用引起的振动模泛频也携带有大量的振动能,这些泛频也对分子振动能量传递产生重要影响.     

Intermodulation of transverse magnetoresistance oscillations in structures with strong intersubband interaction

In the Shubnikov–de Haas oscillation spectrum of doped InAs/AlSb structures, high-amplitude peaks are established at combination frequencies. It is demonstrated that they are caused by a significant contribution of intersubband scattering to the processes of electron-electron interaction. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 32–38, December, 2008.     

Vibrational analysis of nitrosamine,a molecule with an almost constant potential along the inversion coordinate

ABSTRACT

The fundamental vibrational transitions of nitrosamine and its doubly deuterated isotopologue have been computed by vibrational configuration interaction theory including up to 6-tuple excitations. The potential energy surface has been represented by an n-mode expansion up to 4-mode couplings terms obtained from explicitly correlated coupled-cluster theory, CCSD(T)-F12a. Very good agreement with experimental data has been been achieved and a number of new assignments is provided.     

Relaxation of a quadrupolar nucleus in a strong magnetic field

Longitudinal relaxation of spin systems (S = 1, 3/2, 3) containing isolated quadrupolar nuclei are studied. The characteristic features of the relaxation behavior are identified in strong magnetic fields in the presence of chemical shift anisotropy. Two mechanisms are established that favor involvement of high rank multipoles in the relaxation process: an autocorrelation mechanism and a cross correlation mechanism. Multipoles of odd rank are involved in the relaxation of nuclei with spin S > 1 as a result of the autocorrelation mechanism (in this case, due to quadrupole interactions). The cross correlation mechanism, due to correlations between the chemical shift anisotropy and the quadrupole interactions, favors the appearance of multipoles of even rank. Expressions are presented for the multipole cross relaxation and longitudinal relaxation rates for spin systems with S = 1, 3/2, 3. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 18–25, January–February, 2006.     

Vibrational studies of polar aprotic molecule in aromatic chemical and isotropic solvents: experimental and quantum chemical investigations

Raman spectroscopic technique has been used to study the intermolecular interactions and dynamics of SO, C―H and CSC stretching modes of dimethyl sulfoxide (DMSO) in binary mixtures using methyl benzene (MBN) and deuterated methyl benzene (MBNd) aromatic solvents. The Raman band of SO stretching mode has been deconvoluted into four distinct bands for neat DMSO as well as in binary mixtures. Deconvoluted bands in neat DMSO were assigned as monomer, cyclic out‐of‐phase, cyclic in‐phase and chain dimers having peak wavenumbers 1069.10, 1056.60, 1041.50 and 1027.30 cm⁻¹ respectively. Peak wavenumber of SO stretching mode shows red shift, while peak wavenumbers of C―H and CSC stretching modes show blue shift with the increase in solvent concentration. The vibrational relaxation phenomena for all the stretching modes have been studied as a function of solvent concentration. Quantum‐chemical calculations have been carried out to gain more insight into the self‐association of DMSO and in interacting environment with the solvents using ab initio and density functional theory method. The ab initio basis set is HF/6‐31 + G (d, p) for the interacting system. The hydrogen bond complexes of DMSO with MBN and MBNd using IEF‐PCM model have been calculated using B3LYP functional and 6‐31 + G(d,p) basis sets. Theoretical calculations have been compared with the experimental findings and we obtained good coherence of the results. Copyright © 2015 John Wiley & Sons, Ltd.     

Molecular interaction of silybin with hyaluronidase: A spectroscopic and molecular docking study

In this study, the molecular interaction of silybin with hyaluronidase was investigated by spectroscopic methods and molecular docking. It was found that silybin had strong ability to quench the intrinsic fluorescence of hyaluronidase by a static quenching procedure. The binding constants were obtained at three temperatures (293, 298, and 310 K). The results of synchronous fluorescence and three-dimensional fluorescence and molecular docking showed that silybin bound into the hyaluronidase cavity site and the binding of silybin to hyaluronidase could induce micro-environmental and conformational changes in hyaluronidase, which resulted in the reduced hyaluronidase activity. The thermodynamic parameter analysis and molecular docking experiments revealed that all types of non-covalent interaction, including hydrogen bonding interaction, van der Waals forces, hydrophobic interaction, and electrostatic interaction were present in the binding process of silybin with hyaluronidase. The results obtained here will provide direct evidence at a molecular level to understand the mechanism of the inhibitory effect of silybin against hyaluronidase.     

石墨烯低温热膨胀和声子弛豫时间随温度的变化规律

考虑到原子非简谐振动和电子-声子相互作用,用固体物理理论和方法研究了石墨烯格林艾森参量和低温热膨胀系数以及声子弛豫时间随温度的变化规律,探讨了原子非简谐振动项对它们的影响.结果表明:1)在低于室温的温度范围内,石墨烯的热膨胀系数为负值,随着温度的升高,其热膨胀系数的绝对值单调增加,室温热膨胀系数为-3.64×10~(-6)K~(-1);2)简谐近似下的格林艾森参量为零.考虑到非简谐项后,格林艾森参量在1.40-1.42之间并随温度升高而缓慢增大,几乎成线性关系,第二非简谐项对格林艾森参量的影响小于第一非简谐项;3)石墨烯声子弛豫时间随着温度的升高而减小,其中,温度很低(T10 K)时变化很快,此后变化很慢,当温度不太低(T300 K)时,声子弛豫时间与温度几乎成反比关系.     

电声子相互作用对量子点分子中单电子隧穿的影响

研究了双量子点系统中的电子隧穿动力学过程，在考虑电子与声子相互作用的情况下用基于 正则变换的微扰方法解析地得到了电子动态隧穿电流的表达式. 并且详细分析电子与声子耦 合引起的退相干问题，在此基础上指出了可能的退耦机理. 关键词： 电声子相互作用 双量子点 隧穿     

Nonmonotonic external field dependence of the magnetization in a finite Ising model: Theory and MC simulation

Using field theory and Monte Carlo (MC) simulation we investigate the finite-size effects of the magnetization M for the three-dimensional Ising model in a finite cubic geometry with periodic boundary conditions. The field theory with infinite cutoff gives a scaling form of the equation of state where is the reduced temperature, h is the external field and L is the size of system. Below and at the theory predicts a nonmonotonic dependence of f(x,y) with respect to at fixed and a crossover from nonmonotonic to monotonic behaviour when y is further increased. These results are confirmed by MC simulation. The scaling function f(x,y) obtained from the field theory is in good quantitative agreement with the finite-size MC data. Good agreement is also found for the bulk value at . Received 20 July 1999 and Received in final form 11 November 1999     

Effect of the frequency of intramolecular motions on the NMR relaxation in liquid state temperature regime

Equations for the spectral densities of complex motion of a spin pair undergoing internal motion and isotropic/anisotropic overall rotation have been considered. The fluctuations of the interproton distances, caused by internal motion, have been taken into account in the theoretical equations. A method allowing a distinction between the isotropic and the anisotropic overall rotation of molecules has been proposed. The effect of the activation parameters of internal motions (known from the solid state study) on the measured T ₁ relaxation of the ¹³C and ¹H–¹H cross-relaxation rates has been analysed for methyl-β-D-galactopyranoside in DMSO-d6 solution. The conformational trans-gauche jumps of the methylene group are not fast enough to affect the T ₁ value of carbon C6 in the liquid state temperatures regime. Only the methyl group rotation is a very fast internal motion. This motion influences the carbon C7 relaxation and methyl protons–anomeric proton cross-relaxation. The values of interatomic distances between anomeric H(C1) and H(C5) as well as the three methyl protons H(C7) have been calculated from the cross-relaxation rates. The distance H(C1)–H(C7) fluctuates due to the rotation of methyl group. The application of the ‘model-free approach’ to study molecular dynamics in solutions is discussed.     

Electronic Wave-Packets in Integer Quantum Hall Edge Channels: Relaxation and Dissipative Effects

We theoretically investigate the evolution of the peak height of energy-resolved electronic wave-packets ballistically propagating along integer quantum Hall edge channels at filling factor equal to two. This is ultimately related to the elastic scattering amplitude for the fermionic excitations evaluated at different injection energies. We investigate this quantity assuming a short-range capacitive coupling between the edges. Moreover, we also phenomenologically take into account the possibility of energy dissipation towards additional degrees of freedom—both linear and quadratic—in the injection energy. Through a comparison with recent experimental data, we rule out the non-dissipative case as well as a quadratic dependence of the dissipation, indicating a linear energy loss rate as the best candidate for describing the behavior of the quasi-particle peak at short enough propagation lengths.