Properties of the HYSCORE spin echo signal

In hyperfine sublevel correlation spectroscopy (HYSCORE), the finite duration of the microwave pulses leads to an incomplete inversion of the electron spin magnetization by the third pulse, which results in a significant admixture of stimulated ESEEM to HYSCORE ESEEM. This virtually unavoidable contribution of stimulated ESEEM seriously hampers the analysis of the modulation amplitudes in HYSCORE. In this work, we analyze the properties of the spin echo signals contributing to the composite HYSCORE signal. Based on this analysis, we propose the strategies of HYSCORE data acquisition and processing that allow one to practically eliminate the contribution of the stimulated echo and make the HYSCORE ESEEM analyzable in quantitative terms.     

5- and 6-pulse electron spin echo envelope modulation (ESEEM) of multi-nuclear spin systems

In 3-pulse ESEEM and the original 4-pulse HYSCORE, nuclei with large modulation depth (k approximately 1) suppress spectral peaks from nuclei with weak modulations (k approximately 0). This cross suppression can impede the detection of the latter nuclei, which are often the ones of interest. We show that two extended pulse sequences, 5-pulse ESEEM and 6-pulse HYSCORE, can be used as experimental alternatives that suffer less strongly from the cross suppression and allow to recover signals of k approximately 0 nuclei in the presence of k approximately 1 nuclei. In the extended sequences, modulations from k approximately 0 nuclei are strongly enhanced. In addition, multi-quantum transitions are absent which simplifies the spectra. General analytical expressions for the modulation signals in these sequences are derived and discussed. Numerical simulations and experimental spectra that demonstrate the higher sensitivity of the extended pulse sequences are presented.     

OPTESIM, a versatile toolbox for numerical simulation of electron spin echo envelope modulation (ESEEM) that features hybrid optimization and statistical assessment of parameters

Electron spin echo envelope modulation (ESEEM) is a technique of pulsed-electron paramagnetic resonance (EPR) spectroscopy. The analyis of ESEEM data to extract information about the nuclear and electronic structure of a disordered (powder) paramagnetic system requires accurate and efficient numerical simulations. A single coupled nucleus of known nuclear g value (g_N) and spin I = 1 can have up to eight adjustable parameters in the nuclear part of the spin Hamiltonian. We have developed OPTESIM, an ESEEM simulation toolbox, for automated numerical simulation of powder two- and three-pulse one-dimensional ESEEM for arbitrary number (N) and type (I, g_N) of coupled nuclei, and arbitrary mutual orientations of the hyperfine tensor principal axis systems for N > 1. OPTESIM is based in the Matlab environment, and includes the following features: (1) a fast algorithm for translation of the spin Hamiltonian into simulated ESEEM, (2) different optimization methods that can be hybridized to achieve an efficient coarse-to-fine grained search of the parameter space and convergence to a global minimum, (3) statistical analysis of the simulation parameters, which allows the identification of simultaneous confidence regions at specific confidence levels. OPTESIM also includes a geometry-preserving spherical averaging algorithm as default for N > 1, and global optimization over multiple experimental conditions, such as the dephasing time (τ) for three-pulse ESEEM, and external magnetic field values. Application examples for simulation of ¹⁴N coupling (N = 1, N = 2) in biological and chemical model paramagnets are included. Automated, optimized simulations by using OPTESIM lead to a convergence on dramatically shorter time scales, relative to manual simulations.     

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.     

A comment on the theory of one-dimensional mixing-frequency electron spin echo envelope modulation (MIF-ESEEM) spectroscopy

The theory of one-dimensional mixing-frequency electron-spin-echo envelope modulation (MIF-ESEEM) spectroscopy of disordered systems has been revised. In particular, the correct dependence of the position and width of the MIF-ESEEM peaks on the experimental parameters has been obtained, thus providing formulas which enable one to properly interpret the experimental data. The differences with the previously published analyses are discussed. The close relationship with the two-dimensional HYSCORE spectroscopy is remarked on. Experimental examples demostrate the main results.     

Observation of potassium hyperfine interactions in x-irradiated KH2AsO4 through the method of electron spin echo envelope modulation

Hyperfine interaction frequencies of ¹H and ³⁹K nuclei near the AsO^4-₄ radical in X-ray irradiated KH₂AsO₄ (KDA) have been observed through the method of electron spin echo envelope modulation (ESEEM). This method enabled us to record nuclear hyperfine interaction (ENDOR-like) spectra around the ferroelectric phase transition of KDA for the first time. The ESEEM spectrum of ³⁹K exhibits a clear change when passing the ferroelectric phase transition temperature, but that of close protons does not. The result for close protons is in agreement with the symmetry breaking of the AsO^4-₄ site as observed via the EPR spectrum [5]. Finally, at 4.2 K the hyperfine interaction parameters of a ³⁹K nucleus near the AsO^4-₄ unit could be determined through the ESEEM method.     

浅海小目标前向散射的非互易时反检测方法

将无源非互易时反(NRTR)用于浅海小目标前向散射探测海上实验研究,提出了一种基于频域加权松弛的信道估计算法(WRELAX)和时反方法相结合的小目标探测算法(WRELAX-NRTR)。该算法采用高精度的信道响应估计实现信道的空-时匹配,利用目标引起的时反声场结构的畸变检测前向散射信号对声场的扰动实现目标探测,并通过阈值法实现目标判决。在15~30 kHz的信号频率范围内进行海上实验,数据的处理结果表明,提出的WRELAX-NRTR探测算法与传统的NRTR算法相比,环境背景的扰动幅度从10 dB减小到4 dB,从而降低了虚警率,另外该算法对海洋环境噪声、目标聚焦深度、目标穿越距离和信道动态变化等均具有良好的鲁棒性。     

The effect of k-cubic Dresselhaus spin–orbit coupling on the decay time of persistent spin helix states in semiconductor two-dimensional electron gases

We study the theoretical effect of k-cubic （i.e, cubic-in-momentum） Dresselhaus spin-orbit coupling on the decay time of persistent spin helix states in semiconductor two-dimensional electron gases. We show that the decay time of persistent spin helix states may be suppressed substantially by k-cubic Dresselhaus spin-orbit coupling, and after taking the effect of k-cubic Dresselhaus spin-orbit interaction into account, the theoretical results obtained accord both qualitatively and quantitatively with other recent experimental results.     

Temperature-dependent electron spin polarization of the triplet state of the primary donor in photosynthetic reaction centers ofRhodopseudomonas viridis: A time-resolved EPR study of single crystals and solid solution

The electron spin polarization (ESP) of triplet of the primary donor (³P) ofRhodopseudomonas viridis reaction centers (RCs) is anomalous at temperatures above 25 K, i.e. the steady-state ESP changes from AEEAAE to AEAEAE. Fast, time-resolved EPR measurements in solid solution and single crystals of RCs show that this phenomenon results most probably from fast anisotropic spin-lattice relaxation in the radical pair triplet state (k _r≈ 5·10⁹s^?1 at 25 K).     

多尺度策略和替代数据检验——HRV时间不可逆性分析的两个要素

本文通过应用基于多尺度思想的（Pm,Gm）平面法和替代数据检验,对来自于不同人群以及来自于健康年轻人清醒、睡眠状态下的心率变异性（heartratevariability,HRV）进行了时间不可逆性分析．结果表明：健康成人的HRV普遍存在着时间不可逆性,而随着疾病的出现,这种不可逆性减弱但并非消失,大部分（超过75％）充血性心力衰竭患者的HRV仍具有时间不可逆性：健康年轻人的HRV不可逆性存在着昼夜节律和显著的昼夜差异,夜间睡眠时不可逆性更强．我们认为：由于产生HRV的心脏动力系统具有复杂的延迟特性,在对HRV进行时间不可逆分析时,为了得到更可靠的结论,建议采用多尺度策略以及进行替代数据检验．综合考虑上述两个因素的分析方法也较好地统一了已有报道的不同结论．     

Performance of a four‐element Si drift detector for X‐ray absorption fine‐structure spectroscopy: resolution, maximum count rate,and dead‐time correction with incorporation into the ATHENA data analysis software

The performance of a four‐element Si drift detector for energy‐dispersive fluorescence‐yield X‐ray absorption fine‐structure measurements is reported, operating at the National Institute of Standards and Technology beamline X23A2 at the National Synchrotron Light Source. The detector can acquire X‐ray absorption fine‐structure spectra with a throughput exceeding 4 × 10⁵ counts per second per detector element (>1.6 × 10⁶ total counts per second summed over all four channels). At this count rate the resolution at 6 keV is approximately 220 eV, which adequately resolves the Mn Kα and Kβ fluorescence lines. Accurate dead‐time correction is demonstrated, and it has been incorporated into the ATHENA data analysis program. To maintain counting efficiency and high signal to background, it is suggested that the incoming count rate should not exceed ～70% of the maximum throughput.