Molecular dynamics of amide ions in potassium amide (KNH2) studied with orientation-dependent deuterium spin lattice relaxation

The reorientational molecular dynamics of the amide ions were investigated in three different phases of KND2 by means of 2H NMR line-shape analyses of solid-echo, T1Z as well as T1Q distorted spectra in a temperature range of 80-420 K. The correlation times of the amide dynamics cover roughly eight decades in this temperature range. Due to the nonzero asymmetry parameter (eta approximately 0.2) of the electric field gradient tensor the calculation of the orientation-dependent spectral densities Jm(theta, phi) required for the interpretation of the T1Z and T1Q distorted spectra cannot be simplified as in the case eta = 0 and a numerical approach was used for the calculation of Jm(theta, phi), which allows a maximum flexibility for simulating different models of motion. The amide ion dynamics in the low-temperature phase can be described as a superposition of a thermally activated large angle jump of the amide ions about their two-fold axes in an asymmetric four-well potential and strongly anisotropic molecular librations. The asymmetry of the potential surface of the jump process was found to be a function of temperature. Activation energy EA, attempt frequency tau0(-1) and DND bond angle epsilon were determined to 15.5(2) kJ/mol, 62(6) x 10(12) s(-1) and 104.7(3) degrees. In the middle- and high-temperature phases the amide ions perform 90 degrees jumps about the crystallographic four-fold axes. For the high-temperature modification the correlation times were observed to follow an Arrhenius law with EA = 6.3(2) kJ/mol and tau0(-1) = 32(3) x 10(12) s(-1).     

强外电场作用下CCl3F物理特性与光谱

运用密度泛函理论在6-311++G（d,p）基组上进行优化并在x轴方向增加电场（F=-0.025~0.025 a.u.）,对CCl₃F分子结构、偶极矩、总能量、电荷分布和能隙、C-Cl键特征吸收峰进行研究.结果表明：随着外场强度的增加,C-Cl键键长逐渐减小,偶极矩先减小后增大,总能量先增大后减小,Cl原子的电荷分布逐渐增大,当F=-0.015 a.u.时,由负电性转变为正电性,达到新的亲核亲电反应作用点.而能隙在没有外加电场时也达到最小值,此时最容易发生电场降解反应.C-Cl键的红外特征吸收峰随着负电场的增强出现蓝移.     

Can a linearly polarized light beam polarize atomic spin?

Lax et al. [Phys. Rev. 11 (1975) 1365] discovered that a light beam in vacuum is not a transverse wave but does have a longitudinal field component. We investigate atomic and molecular electric dipole transitions induced by such a light beam, in particular, linearly polarized in a transverse plane. We derive the selection rules and the transition rates for various quantization axes using the paraxial approximation up to the first order of 1/kw, where k is the wave number and w is the transverse size of the light beam. The light beam is able to yield atomic spin polarization in the direction perpendicular to both the optical axis and the transverse electric field, and its magnitude is approximately 1/kw times that generated by a circularly polarized light wave with the similar intensity.     

Dipole capture of a slow electron by a water cluster

It is shown that the anomalously large cross section for attachment of a slow electron to a water cluster (H₂O) _n≥50 that is observed in molecular-beam experiments may be explained by the capture of the electron by a long-range field of the permanent electric dipole moment of the cluster. The cross section values are used to estimate the dipole moment of the cluster as a function of its diameter n. The values obtained significantly exceed the random dipole moments in the case of the proton-disordered cluster structure and indicate the ferroelectric ordering of the orientations of dipole moments of the molecules included in the cluster.     

Measurement of the electric dipole moment of NO (X2 Π ν = 0,1) by mid-infrared laser magnetic resonance spectroscopy

A pair of parallel Stark plates are added to a CO laser magnetic resonance spectrometer to apply electric field in the absorption cell. This apparatus is used to measure the molecular electric dipole moment via Zeeman and Stark effects simultaneously. The saturated absorption spectra of NO (X²Π_3/2, ν = 1 ← 0) was observed and the electric dipole moments of NO were directly measured in the presence of an electric field. The dipole moments are determined as μ₀(ν = 0) = 0.1595(15) D, μ₁ (ν = 1) = 0.1425(16) D. The electric dipole moment of the vibrationally excited state (ν = 1) is determined for the first time. The dependence of the electric dipole moments on its nuclear distances is interpreted.     

Cl nuclear quadrupole resonance studies of molecular motions of ClO3 and water diffusion in Ca(ClO3)2·2H2O

A ³⁵Cl nuclear quadrupole resonance (³⁵Cl-NQR) investigation of polycrystalline Ca(ClO₃)₂·2H₂O is described. The ³⁵Cl-NQR frequencies (ν_Q) for two resonance lines (ν_Q1 and ν_Q2), the spin lattice relaxation time (T_1Q) for ν_Q2 only and the line width δν_Q2 were measured in the temperature range 292–345 K, except for the frequency measured up to 455 K. The observed decrease in the resonance frequencies with increasing temperature permitted the determination of the frequencies of librations of the ClO₃⁻ ion about two axes perpendicular to the three-fold axis of the ion mainly responsible for this effect. The temperature dependence of the relaxation time T_1Q proved the occurrence of water diffusion and hindered rotation of ClO₃⁻ ions. The activation energies of these two molecular motions were determined, and their effect on the electric field gradient at the site of a chlorine nucleus was discussed. Temperature measurements of the line width δν_Q2 confirmed the conclusions drawn from the analysis of T_1Q(T).     

铁电体中偶极子的滞后对剩余极化的影响

铁电体的剩余极化强度随温度降低而下降的特性引起了人们对铁电体存储数据失效的担心.运用铁电体的唯象理论和偶极子对交变电场的响应,提出了在电滞回线测量中偶极子的滞后冷冻效应模型,对极化的低温退化现象做了合理解释:温度下降导致吉布斯自由能势垒增大,致使偶极子对交变电场的响应时间延长.引入响应的滞后因子发现,极化强度随温度降低会出现峰值,在低温下降直至为零,可用偶极子的滞后与冻结效应描述.详细研究结果表明:因材料组份变化导致热力学参量的变化是重要因素:铁电-顺电相变中软模系数的增大会导致剩余极化峰移向高温;铁电性的增强,温度极化系数的增大和耐压强度或饱和电场的增强均会抑制滞后效应,从而使低温滞后效应移向低温.运用导出的公式数值模拟Ba Ti O_3/Bi Sc O_3复合陶瓷剩余极化强度的实验结果发现,Bi Sc O3含量的增加,使居里温度略有减小,但导致了软模系数较大幅度的增加,其结果是使偶极子的滞后效应发生在较高的温度.软模系数与铁电体的极化特性、铁电性、介电性和力学性均密切相关.研究结论表明:在低温下铁电体的铁电性没有失效,偶极子的低温冻结效应更有利于铁电体长久地保存数据.     

偏置电场对聚对苯乙烯激发态弛豫特性的影响

为探讨洞悉电场对有机发光二极管电致荧光量子效率的影响,通过激发-探测超快光谱技术研究了激子在电场下的瞬态行为.与单重态激子相应的激发态在230 μJ/cm2激发强度下,显示了快慢两个弛豫过程. 快慢组分的权重因子及快组分弛豫时间常数是电场相关的, 在6.4×10⁵ V/cm的电场下,与无偏置电场相比,激子的快组分弛豫时间加速,快组分的权重因子由22%增加为72%,约50%的初始激子又通过电场而离解. 慢组分是电场无关的,其弛豫时间常数为890 ps. 实验结果还揭示了由激发光所产生的长程声学声子,其声速为17 /ps. 关键词： 聚对苯乙烯 超快光谱 激子 有机发光二极管     

Nuclear magnetic resonance relaxometry of the normal heart: Relationship between collagen content and relaxation times of the four chambers

The use of nuclear magnetic resonance (NMR) relaxation time measurements for characterization of abnormal cardiac tissue depends upon knowledge of variations of relaxation times of normal myocardium and determinants of these variations. We calculated in vitro NMR T₁ and T₂ relaxation times of canine myocardium from the four cardiac chambers, and determined hydroxyproline concentration (as a measure of collagen) and percent water content of the samples. We found both water content and T₁ relaxation time of the right ventricle to be significantly greater than the left atrium (p < 0.05). T₂ relaxation time of the left ventricle was found to be shorter than each of the other three chambers (p < 0.05). There were significant correlations between the spin-lattice relaxation time and both percent water content (r = 0.58) and hydroxyproline concentration (r = 0.45). A significant correlation was also found between T₂ relaxation time and hydroxyproline concentration (r = 0.49). When T₁ and T₂ were adjusted for water and hydroxyproline content, there was no longer any evidence for significant interchamber differences for either T₁ or T₂. These data suggest that differences in NMR relaxation times exist among the four chambers of the normal canine heart. Furthermore, a major determinant of myocardial spin-lattice relaxation time is tissue water content while both collagen content and percent water content significantly contribute to variability in cardiac chamber T₂ relaxation times.     

Study of vibrational relaxation and molecular reorientation in liquids: a Raman spectroscopic study

The vibrational relaxation and molecular reorientational processes in liquids have been studied in some carbonyl‐containing molecules using the acetonitrile (ACN) solvent. The vibrational and reorientational processes have been studied in correspondence with correlation times. The screening effect due to dielectric has been studied and the Onsager reaction field model has been tested. The study shows that repulsive types of intermolecular forces play an important role in complex systems. Copyright © 2010 John Wiley & Sons, Ltd.     

Bound water: Evidence from and implications for the dielectric properties of aqueous solutions

Broadband dielectric spectra of a variety of aqueous solutions are evaluated as to indications of water that may be considered bound. Static permittivity decrements due to depolarizing internal electric fields, from kinetic depolarization, as well as from dielectric saturation are discussed. The latter effect reflects the preferential orientation of water permanent dipole orientations within strong Coulombic field of small ions, especially multivalent cations. Such water may be considered bound even though rapid rotations around the orientation of the electric dipole moment are definitely possible and also a fast exchange of water molecules between the hydration region and the bulk may take place. Water exhibiting large dielectric relaxation times, as typical for regions with large local concentration of foreign matter, may also be named bound. However, no clear evidence for interaction energies exceeding the hydrogen bond energy of pure water has been found. Rather enhanced relaxation times at low water content reflect the small concentration of hydrogen bonding sites and thus low probability density for the formation of a new hydrogen bond. Potential interferences of the water relaxation with relaxations from other molecules or from ionic structures are mentioned briefly.     

Dipole relaxation in weak and strong fields

The process of dipole relaxation in a homogeneous dielectric is studied on the basis of a two-state dipole model. The external field is not assumed to be weak. Two types of applied electric fields are considered: a linearly increasing field, and a field which changes by steps. At the present time pulsed electric fields have found wide application in electron-ion technology.Translated from Izvestiya VUZ. Fizika, No. 1, pp. 95–100, January, 1972.     

Investigation on the Cs 6S1/2 to 7D electric quadrupole transition via monochromatic two-photon process at 767 nm

We experimentally demonstrate the cesium electric quadrupole transition from the 6S_1/2 ground state to the 7D_3/2,5/2 excited state through a virtual level by using a single laser at 767 nm. The excited state energy level population is characterized by varying the laser power, the temperature of the vapor, and the polarization combinations of the laser beams. The optimized experimental parameters are obtained for a high resolution transition interval identification. The magnetic dipole coupling constant A and electric quadrupole coupling constant B for the 7D_3/2,5/2 states are precisely determined by using the hyperfine levels intervals. The results, A = 7.39 (0.06) MHz, B = −0.19 (0.18) MHz for the 7D_3/2 state, and A = −1.79 (0.05) MHz, B =1.05 (0.29) MHz for the 7D_5/2 state, are in good agreement with the previous reported results. This work is beneficial for the determination of atomic structure information and parity non-conservation, which paves the way for the field of precision measurements and atomic physics.     

Dielectric relaxation spectrum of water studied by the site—site generalized Langevin/modified mode-coupling theory

The dielectric relaxation spectrum of water is calculated from the site-site generalized Langevin/modified mode-coupling theory. The main part of the relaxation follows the Debye-type function, and a small deviation from the Debye relaxation is found on the high-frequency side. This tendency is consistent with recent experiments, although the absolute relaxation time does not agree with the experimental value quantitatively. The time development of the longitudinal polarization function resembles the dielectric part of the memory function, and we consider that this is because the dielectric friction dominates the collective reorientation of the dipole moment of water. We performed calculations with different dielectric constants using the reference interaction-site model integral equation, and found that the large gap between the time scales of the dielectric relaxation and the longitudinal polarization relaxation causes the Debye-type dielectric relaxation in our theory when the dielectric friction is dominant in the friction on the collective reorientation of the dipole moment. Namely, the longitudinal polarization relaxation is fast enough to be considered as a white noise to the dielectric relaxation process, so that the relaxation becomes a Markov process. The large gap between the two relaxation times originates from a large local field correction owing to the large dielectric constant of water. It is also suggested that the deviation from the Debye relaxation at the high-frequency side is the manifestation of the slow memory caused by the long-time part of the longitudinal polarization relaxation in the low-wavenumber region.     

Spin relaxation and linear-in-electric-field frequency shift in an arbitrary, time-independent magnetic field

A method is presented to calculate the spin relaxation times T(1), T(2) due to a non-uniform magnetic field, and the linear-in-electric-field precession frequency shift δω(E) when an electric field is present, in the diffusion approximation for spins confined to a rectangular cell. It is found that the rectangular cell geometry admits of a general result for T(1), T(2), and δω(E) in terms of the spatial cosine-transform components of the magnetic field. The result is applied to the case of a permanently-magnetized dipole impurity near the cell.     

Electron polarization in quantum wells in a strong variable field

The wave function of an electron in a symmetric double quantum well placed in a strong time-periodic electric field is found, expressions for quasienergy functions are derived, and the dependence of the dipole moment on the average electric field is analyzed for the case where the average field remains constant. In the case of slow monotonic variation of the “constant” component of the electric field, the Schro dinger equation is solved by the WKB method. It is found that the dependence of the dipole moment on the average field is of a clearly nonlinear almost-periodic nature and that in the event of adiabatic monotonic variation of the average field there is a periodic relocation of the electron density from well to well with a small frequency proportional to the rate of variation of the average field. Zh. éksp. Teor. Fiz. 116, 217–235 (July 1999)     

Electromagnetically induced transparency in novel dual-band metamaterial excited by toroidal dipolar response

We demonstrated a novel metamaterial with dual-band electromagnetically induced transparency(EIT)via simulation,experiment and numerical analysis,with resonance frequencies of the trans-parency peaks of 7.60 and 10.27 GHz.The E-εmetamaterial unit cells were composed of E-shaped and e-shaped patterns.By analyzing the surface current distribution and the magnetic field,we qualitatively verified the toroidal dipole response in the E-εmetamaterial at 10.27 GHz.Meanwhile,by calculating the multipole's radiated power,we found that the two transparency peaks were due to the excitation of the electric and toroidal dipole responses.By changing the incident angle from 0°to 60°,we observed changes in transmission spectra,and the quality factors(Q-factors)of the two transparency peaks increased.In addition,the proposed E-εmetamaterial can be designed to act as a refractive index sensor or other electronic equipment for the control of electromagnetic waves.     

Nonselective excitation of pulsed ELDOR using multi-frequency microwaves

The use of a polychromatic microwave pulse to expand the pumping bandwidth in pulsed electron-electron double resonance (PELDOR) was investigated. The pumping pulse was applied in resonance with the broad (～100 mT) electron paramagnetic resonance (EPR) signal of the manganese cluster of photosystem II in the S2 state. The observation pulses were in resonance with the narrow EPR signal of the tyrosine radical, YD·. It was found that in the case of the polychromatic pumping pulse containing five harmonics with the microwave frequencies between 8.5 and 10.5 GHz the PELDOR effect corresponding to the dipole interaction between the Mn cluster and YD· was about 2.9 times larger than that achieved with a monochromatic pulse. In addition to the dipolar modulation, the nuclear modulation effects were observed. The effects could be suppressed by averaging the PELDOR trace over the time interval between the observation microwave pulses. The polychromatic excitation technique described will be useful for improving the PELDOR sensitivity in the measurements of long distances in biological samples, where the pair consists of a radical with a narrow EPR spectrum and slow phase relaxation, and a metal center that has a broad EPR spectrum and a short phase relaxation time.     

High-energy approximations to nuclear scattering: W. E. Frahn and B. Schürmann. Physics Department,University of Cape Town,Rondebosch (Cape), South Africa

The effect of slow rotation on the dipole magnetic field of neutron stars is studied. It is shown that the differential rotation of inertial frames produced by the effect of “dragging of inertial frames” induces an additional component of electric field outside the star. This new component, as well as the usual electromagnetic components, vanishes as in the limit of collapse of a star to its Schwarzschild radius. For typical neutron stars, the electric quadrupole moment is about half that obtainable from a flat space analysis.     

Landau coefficients and the critical electric field in a KDP crystal

Analytical expressions for the Landau coefficients of deuterated potassium dihydrogen phosphate (DKDP) crystal are obtained in a four-particle cluster approximation. The critical electric field strengths calculated within the phenomenological and microscopic theories for DKDP are compared to experimental data. Calculations of the critical electric field in potassium dihydrogen phosphate (KDP) crystal in the cluster approximation with allowance for proton tunneling on hydrogen bonds allows us to determine the tunneling constant and the geometric factor associated with the change in the effective dipole moment upon deuteration. Good agreement with the experimental data is obtained only for positive values of the long-range interaction parameter.