Determination of atomic positions of point defects in solids by ENDOR

The experimental results which are obtained from electron nuclear double resonance (ENDOR) of point defects in solids are briefly reviewed. From the relation between the experimental superhyperfine and quadrupole interaction tensors and the spin density distribution and charge density distribution, the details of the microscopic structure and thus the positions of atoms can in principle be obtained. For this, in general, a precise theory of the defect wave function is required. However, there are many cases in which simple approximations to the wave function can be used to determine atomic positions rather well. This is illustrated with several examples, mainly from ionic solids. The particular difficulties encountered in semiconductors and the influence of dynamical effects are also discussed.     

Spin diffusion of dipolar energy in NQR

The theory of spin diffusion was extended to the case of nuclear dipolar order in solids containing paramagnetic impurities and nuclei with spin I > 1/2 having nuclear quadrupole moment. We show that spin diffusion process of dipolar order takes place in solids containing paramagnetic impurities. At the start of relaxation process, the direct relaxation regime is realized with non-exponential time dependence. Then the relaxation regime will be changed to diffusion-limited one. Using obtained expressions for the spin lattice relaxation times for these two relaxation regimes, the diffusion coefficient of the dipolar order in nuclear quadrupole resonance can be estimated from experimental data.     

Nuclear magnetism of liquid systems in the earth field range

In this paper we review the used techniques and the main results obtained by nuclear magnetism in the low field range. After a brief survey of the characteristics of nuclear magnetism in low fields, the experimental techniques are described: obtaining constant and homogeneous fields, resonance experiments and pulse techniques (free precession and spin echoes). The most important results include: studies of line-width and shape in the liquid state, some features of the interaction between electromagnetic field and nuclear moments (spin echoes, non-resonant excitation) and a new possible investigation of microscopic structure and dynamics in the liquid state (indirect spin-spin interaction and dispersion of relaxation times).     

Spectral densities and nuclear spin relaxation in solids

We investigate the properties of ten spectral densities relevant for nuclear spin relaxation studies in solids. This is preceded by a brief review of nuclear spin relaxation in solids which includes a discussion of the appropriate spin-dependent interactions and the various relaxation rates which can be measured. Also, the link between nuclear spin relaxation and dielectric relaxation is discussed. Where possible and/or appropriate each of the spectral densities is expressed as a continuous distribution of Bloembergen-Purcell-Pound (or Debye) spectral densities 2ξ /(1 + ξ² ω²) for nuclear Larmor angular frequency ω and correlation time ξ. The spectral densities are named after their originators or the shape of the distributions of correlation times or both and are (1) Bloembergen-Purcell-Pound or δ-function, (2) Havriliak-Negami, (3) Cole-Cole, (4) Davidson-Cole, (5) Fang, (6) Fuoss-Kirkwood, (7) Bryn Mawr, (8) Wagner or log-Gaussian, (9) log-Lorentzian, and (10) Fröhlich or energy box. The Havriliak-Negami spectral density is related to the Dissado-Hill theory for dielectric relaxation. The spectral densities are expressed in a way which makes them easy to compare with each other and with experimental data. Many plots of the distributions of correlation times and of the spectral densities vs. various correlation times characterizing the distributions are given.     

Spin diffusion and nuclear spin-lattice relaxation in irradiated solids: a multiple-pulse NQR study

We present a detailed theoretical and experimental NQR multiple-pulse spin-locking study of spin-lattice relaxation and spin diffusion processes in the presence of paramagnetic impurities in solids. The relaxation function of the nuclear spin system at the beginning of the relaxation process is given by exp , where T_1ρ is spin-lattice relaxation time in rotating frame and =d/6, d is the sample dimensionality. Then the relaxation proceeds asymptotically to an exponential function of time, which was attributed to the spin-diffusion regime. Using the experimental data obtained from the analysis of those two relaxation regimes in γ-irradiated powdered NaClO₃, spin diffusion coefficient has been determined and the radius of the diffusion barrier has been estimated.     

Studies of magnetism by nuclear orientation and NMRON

Low temperature nuclear orientation (NO) and nuclear magnetic resonance on oriented nuclei (NMRON) are used to investigate the magnetic properties of solids, and are especially useful when high sensitivity is required, for example in the study of small or dilute systems. Measurement of the static hyperfine interaction and the nuclear spin-lattice and spin-spin relaxation times T ₁ and T ₂ yield information about the electronic magnetization and spin dynamics, respectively. A number of NMRON techniques are available and their application to the study of magnetism will be briefly discussed. In particular, the pulsed technique has been shown to be effective for studying insulators. Recent NO and NMRON measurements, primarily on insulating magnets and magnetic multilayers, will be reviewed. Spins of stable isotopes can also be investigated using NMR thermally detected by NO (NMR-TDNO), and this method, in combination with NMRON, has been recently applied in both metals and insulators to obtain information about nuclear spin-spin couplings, “frequency pulling” and nuclear magnons. This revised version was published online in August 2006 with corrections to the Cover Date.     

Anisotropic relaxation and motion of half-integer quadrupole nuclei studied by central transition nuclear magnetic resonance spectroscopy

An efficient theoretical formalism and advanced experimental methods are presented for studying the effects of anisotropic molecular motion and relaxation on solid-state central transition NMR spectra of half-integer quadrupole nuclei. The theoretical formalism is based on density operator algebra and involves the stochastic Liouville–von Neumann equation. In this approach the nuclear spin interactions are represented by the Hamiltonian while the motion is described by a discrete stochastic operator. The nuclear spin interactions fluctuate randomly in the presence of molecular motion. These fluctuations may stimulate the relaxation of the system and are represented by a discrete relaxation operator. This is derived from second-order perturbation theory and involves the spectral densities of the system. Although the relaxation operator is valid only for small time intervals it may be used recursively to obtain the density operator at any time. The spectral densities are allowed to be explicitly time dependent making the approach valid for all motional regimes. The formalism has been applied to simulate partially relaxed central transition ¹⁷O NMR spectra of representative model systems. The results have revealed that partially relaxed central transition lineshapes are defined not only by the nuclear spin interactions but also by anisotropic motion and relaxation. This has formed the basis for the development of central transition spin-echo and inversion-recovery NMR experiments for investigating molecular motion in solids. As an example we have acquired central transition spin-echo and inversion-recovery ¹⁷O NMR spectra of polycrystalline cristobalite (SiO₂) at temperatures both below and above the α–β phase transition. It is found that the oxygen atoms exhibit slow motion in α-cristobalite. This motion has no significant effects on the fully relaxed lineshapes but may be monitored by studying the partially relaxed spectra. The α–β phase transition is characterized by structural and motional changes involving a slight increase in the Si–O–Si bond angle and a substantial increase in the mobility of the oxygen atoms. The increase in the Si–O–Si angle is supported by the results of ¹⁷O and ²⁹Si NMR spectroscopy. The oxygen motion is shown to be orders of magnitude faster in β-cristobalite resulting in much faster relaxation and characteristic lineshapes. The measured oscillation frequencies are consistent with the rigid unit mode model. This shows that solid-state NMR and lattice dynamics simulations agree and may be used in combination to provide more detailed models of solid materials.     

Surface analysis by means of magnetic resonance techniques

Both electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopy have been widely used for the analysis of adsorbed atoms, molecules, ions, and defects on surfaces. In this review we wish to describe a number of representative applications of the two techniques, which will illustrate the types of systems that have been studied and will point out some of the more recent developments in the field. Surface analysis will be treated in a rather broad sense in that the electronic structure, motion, and reactivity of surface species will be covered, as well as their identification and quantitative determination.     

基于金刚石氮-空位色心的精密磁测量

磁是一种重要的物理现象,对其进行精密测量推动了许多科技领域的发展.各类测磁技术,包括霍尔传感器、超导量子干涉仪、自旋磁共振等,都致力于提升空间分辨率和灵敏度.近年来,金刚石中的氮-空位色心广受关注.这一固态单自旋体系具有许多优点,例如易于初始化和读出、可操控、具有较长相干时间等,这使得它不仅在量子信息、量子计算等领域崭露头角,而且在量子精密测量上显现出巨大的应用前景.基于氮-空位色心,利用动力学解耦、关联谱等技术,已实现若干高灵敏度、高分辨率的微观磁共振实验,其中包括纳米尺度乃至单分子、单自旋的核磁共振和电子顺磁共振.氮-空位色心也可以用于微波和射频信号的精密测量.本文对围绕上述主题开展的一系列研究工作进行综述.     

The formation of defects in Si under the radiation enhanced diffusion conditions

A review is given of recent developments in the study of magnetic (localized) photo-excitations in ionic solids. Emphasis will be on three topics: (i) the importance of magnetic properties in the structural characterization of defects, (ii) photo-chemical reactions as revealed from magnetic interactions in point defects, and (iii) energy and phase relaxation dynamics in photo-excited colour centres as probed from magnetic transients. In our survey we will focus on defects photo-excited to phosphorescent triplet states. In discussing a number of dynamical processes, some attention is given to the application of (optical-microwave) coherence spectroscopy which holds considerable promise for future work.     

Spin–Spin Interactions and Nuclear Magnetic Relaxation in Magnetic Solids

The influence of the orientational fluctuations of the electronic magnetization, which modulate nuclear spin–spin interactions (Suhl–Nakamura and dipole–dipole), on the spin-lattice relaxation of magnetic nuclei with spin I = 1/2 in the magnetically ordered solids has been investigated. It has been shown that this mechanism of the spin-lattice relaxation is less effective in comparison with the process of spin-lattice relaxation caused by the direct fluctuations of hyperfine fields, which appear when there are the fluctuations of electronic magnetization direction.     

Feasibilities of nuclear techniques for the study of molecular defects in metals and semiconductors

Nuclear techniques, like Mössbauer effect and perturbed γγ angular correlation spectroscopy (PAC), have proven themselves to be sensitive tools for labelling and identifying probe atom-defect complexes. In these experiments, the “molecular defect” is investigated via the nuclear hyperfine interaction, which is measured at the site of the radioactive probe atom. Here, we shall put the emphasis on the PAC spectroscopy, which often uses¹¹¹In/¹¹¹Cd as radioactive probe atom. In metals, based on the identification of simple probe atom-defect pairs, the agglomeration of defects after cold-working and the interaction of vacancies with He atoms will be discussed. In semiconductors, it will be focussed on the interaction between dopant atoms, which strongly determines the electrical properties of these materials.     

13C spin-lattice relaxation in natural diamond: Zeeman relaxation at 4.7 T and 300 K due to fixed paramagnetic nitrogen defects

13C spin-lattice relaxation times in the laboratory frame, ranging from 1.4 to 36 h, have been measured on a suite of five natural type Ia and Ib diamonds at 4.7 T and 300 K. Each of the diamonds contains two types of fixed paramagnetic centers with overlapping inhomogeneous electron paramagnetic resonance (EPR) lines. EPR techniques have been employed to identify these defects and to determine their concentrations and relaxation times at X-band. Spin-lattice relaxation behavior of 13C in diamonds containing paramagnetic P1, P2, N2. and N3 centers are discussed. Depending on the paramagnetic impurity types and concentrations present in each diamond, three different nuclear spin-lattice relaxation (SLR) paths exist, namely that due to electron SLR mechanisms and two types of three-spin processes (TSPs). The one three-spin process (TSP1) involves a simultaneous transition of two electron spins belonging to the same hyperfine EPR line and a flip of a 13C spin, while the other process (TSP2) involves two electron spins belonging to different hyperfine EPR lines and a 13C spin. It is shown that the thermal contact between the 13C nuclear Zeeman and electron dipole-dipole interaction reservoirs is field dependent, thus forming a bottleneck in the 13C relaxation path due to TSP1 at high magnetic fields.     

Beyond the T1 limit: singlet nuclear spin states in low magnetic fields

Low-field nuclear spin singlet states may be used to store nuclear spin order in a room temperature liquid for a time much longer than the spin-lattice relaxation time constant T1. The low-field nuclear spin singlets are unaffected by intramolecular dipole-dipole relaxation, which is generally the predominant relaxation mechanism. We demonstrate storage of nuclear spin order for more than 10 times longer than the measured value of T1. This phenomenon may facilitate the development of nuclear spin hyperpolarization methods and may allow the study of motional processes which occur too slowly for existing NMR techniques. This is the first time that the memory of nuclear spins has been extended well beyond the T1 limit in a system lacking intrinsic magnetic equivalence.     

Spin-wave description of nuclear spin-lattice relaxation in Mn12O12 acetate

In response to recent nuclear-magnetic-resonance (NMR) measurements on the molecular cluster Mn12O12 acetate, we study the nuclear spin-lattice relaxation rate 1/T(1), developing a modified spin-wave theory. Our microscopic new approach, which is distinct from previous macroscopic treatments of the cluster as a rigid spin of S=10, not only excellently interprets the observed temperature and applied-field dependences of 1/T(1) for 55Mn nuclei but also strongly supports the 13C NMR evidence for spin delocalization over the entire molecule.     

New Methods for Detection of 14N NQR Frequencies

Nitrogen atoms are present in a number of solid explosives and illicit substances. The nuclear quadrupole resonance (NQR) spectra and spin?Clattice relaxation of the nitrogen atomic nucleus ¹⁴N can be used to characterize these compounds and to distinguish between possible crystal polymorphs. After the characteristic ¹⁴N NQR frequencies and spin?Clattice relaxation rates in a compound are determined, NQR can be used to detect this compounds and, in case of crystal polymorphs, also to determine the method of preparation. The ¹⁴N NQR frequencies and spin?Clattice relaxation rates are measured either by pulse NQR or by nuclear quadrupole double resonance (NQDR) based on magnetic field cycling. Here, we discuss several ¹H?C¹⁴N NQDR techniques which can be used to measure the ¹⁴N NQR frequencies and spin?Clattice relaxation rates under various experimental conditions. Some characteristic applications of these techniques are presented and discussed in details.     

Application of field-cycling NMR relaxometry to the study of ultrasound-induced effects in the molecular dynamics and order of mesomorphic materials

A salient characteristic of nuclear magnetic resonance (NMR) techniques is the possibility to scan nuclear spin evolutions within a broad Larmor frequency range. Special instrumentation was developed to extend nuclear spin relaxation studies up to proton Larmor frequencies in the sub-kilohertz regime, a technique known as field-cycling NMR relaxometry. This article refers to an experimental version where the sample under study is selectively subjected to ultrasonic irradiation. The fact that ultrasound couples selectively to the collective dynamics of liquid crystals, offers new insights for the study of the molecular dynamics in these materials using NMR relaxation.     

Force spectroscopy on single passive biomolecules and single biomolecular bonds

This article describes the recent development of the rapidly expanding field of single molecule force spectroscopy. As the advancement of this field was dictated by technical progress, a large part of this review is focussed on methodological aspects. Moreover, several instructive experiments will be presented. However, it is already impossible to cover the whole field in one review article. Experiments on stretching of single polymers, on force induced dissociation of single bonds, and on unfolding of multidomain proteins are covered whereas active molecules (molecular motors) will be excluded. The physical interpretation of the selected experiments is addressed. The connection between the experimental results and the underlying microscopic properties of the molecules and their respective bonds will be discussed. Especially kinetic effects are of high importance for the interpretation of these experiments.     

Nuclear spin relaxation in paramagnetic systems (S>/=1) under fast rotation conditions

A new theoretical model for nuclear spin relaxation in paramagnetic systems in solution has been developed. Fast rotational motion is included in the model, both as a source of modulation of the static zero-field splitting, which provides a mechanism for electron spin relaxation, and as an origin of the stochastic variation of the electron spin-nuclear spin dipole-dipole interaction leading to nuclear spin relaxation. At the limit of low magnetic field, the model is essentially identical to the earlier formulations from our laboratory, but new closed-form expressions are given for the inner- and outer-sphere relaxation at the high-field limit. Numerical comparisons with a general theory are reported for the inner-sphere case. In addition, some nuclear magnetic relaxation dispersion (NMRD) profiles from the literature are considered for systems where experiments have been done with both low-molecular weight paramagnetic complexes and their adducts with proteins. Previously developed theories are used to interpret data for the slowly rotating protein adducts, and good fits of the fast-rotating counterparts are obtained by further adjustment of one or two additional parameters.     

Modulation of the distance dependence of paramagnetic relaxation enhancements by CSA × DSA cross-correlation

Paramagnetic metal ions with fast-relaxing electronic spin and anisotropic susceptibility tensor provide a rich source of structural information that can be derived from pseudo-contact shifts, residual dipolar couplings, dipole-dipole Curie spin cross-correlation, and paramagnetic relaxation enhancements. The present study draws attention to a cross-correlation effect between nuclear relaxation due to anisotropic chemical shielding (CSA) and due to the anisotropic dipolar shielding (DSA) caused by the electronic Curie spin. This CSA x DSA cross-correlation contribution seems to have been overlooked in previous interpretations of paramagnetic relaxation enhancements. It is shown to be sufficiently large to compromise the 1/r6 distance dependence usually assumed. The effect cannot experimentally be separated from auto-correlated DSA relaxation. It can increase or decrease the observed paramagnetic relaxation enhancement. Under certain conditions, the effect can dominate the entire paramagnetic relaxation, resulting in nuclear resonances narrower than in the absence of the paramagnetic center. CSAxDSA cross-correlation becomes important when paramagnetic relaxation is predominantly due to the Curie rather than the Solomon mechanism. Therefore the effect is most pronounced for relaxation by metal ions with large magnetic susceptibility and fast-relaxing electron spin. It most strongly affects paramagnetic enhancements of transverse relaxation in macromolecules and of longitudinal relaxation in small molecules.