Evolution of solid state systems containing mutually coupled dipolar and quadrupole spins: perturbation treatment

Perturbation approach to time evolution of multi-spin systems containing quadrupole and dipolar spins has been presented and discussed. The treatment comprises polarization transfer effects, field-dependent relaxation processes of dipolar as well as quadrupole spins and combined results of both of them. Complete theories dealing with various aspects of the spin dynamic processes have been proposed. Because of an educational character of this paper, relevant assumptions, limitations and even particular steps of the proposed treatments have been discussed in detail. Special emphasis is put on understanding of validity regimes of the perturbation treatment, depending on relative strengths of spin interactions and timescales of relevant motional processes affecting them. Motional regimes required for spins to be involved in essentially different evolution pathways like polarization transfers or relaxation have been illustrated by experimental examples.     

Nuclear spin-lattice relaxation mechanisms in kaolinite confirmed by magic-angle spinning

Spin-lattice relaxation mechanisms in kaolinite have been reinvestigated by magic-angle spinning (MAS) of the sample. MAS is useful to distinguish between relaxation mechanisms: the direct relaxation rate caused by the dipole-dipole interaction with electron spins is not affected by spinning while the spin diffusion-assisted relaxation rate is. Spin diffusion plays a dominant role in ¹H relaxation. MAS causes only a slight change in the relaxation behavior, because the dipolar coupling between ¹H spins is strong. ²⁹Si relaxes directly through the dipole-dipole interaction with electron spins under spinning conditions higher than 2 kHz. A spin diffusion effect has been clearly observed in the ²⁹Si relaxation of relatively pure samples under static and slow-spinning conditions. ²⁷Al relaxes through three mechanisms: phonon-coupled quadrupole interaction, spin diffusion and dipole-dipole interaction with electron spins. The first mechanism is dominant, while the last is negligibly small. Spin diffusion between ²⁷Al spins is suppressed completely at a spinning rate of 2.5 kHz. We have analyzed the relaxation behavior theoretically and discussed quantitatively. Concentrations of paramagnetic impurities, electron spin-lattice relaxation times and spin diffusion rates have been estimated.     

Dynamics of multiple quantum coherences in dipole-coupling spins in solid

A perturbation method deals with dipolar coupling spins in solids is presented. As example of application the method, the multiple-quantum coherence dynamics in clusters of a linear chain of four nuclear spins and a ring of six spins coupled by dipole-dipole interaction are considered. The calculated 0Q and 2Q intensities in a linear chain of four nuclear spins and 6Q intensity in a ring of six spins vs. the duration of the preparation period agree well with the exact solutions (for linear chain of four nuclear spins) and simulation data (for linear chain of four nuclear spins and a ring of six spin).     

Quadrupole relaxation enhancement--application to molecular crystals

A general theory of field dependent spin-lattice relaxation for nuclei of the spin quantum number 1/2 (1H, 19F, 13C) caused by dipole-dipole interactions with neighboring quadrupolar nuclei (nuclei possessing a quadrupolar moment) is presented. The theory is valid for arbitrary motional conditions and should be treated as a quadrupolar counterpart of the paramagnetic relaxation enhancement theory. When the energy level splitting of the dipolar spin (I=1/2) matches one of the transition frequencies of the quadrupolar nuclei one can observe a local enhancement of the dipolar spin relaxation (referred to as "quadrupolar peaks"). To see such effects the dynamics modulating the spin interactions has to be relatively slow. This brings the system beyond the validity range of perturbation approaches and requires the stochastic Liouville equation to be applied. The presented theory describes the quadrupolar relaxation enhancement (QRE) for an arbitrary spin quantum number of the quadrupolar nuclei and includes the asymmetry of the quadrupolar coupling. It has been applied to interpret the shape of magnetization curves (amplitude of 1H magnetization versus magnetic field) for the molecular crystal [C3N2H5]6[Bi4Br18] ([C3N2H5]-imidazolium). The magnetization curves show several dips (local minima) attributed to 1H-14N quadrupolar relaxation enhancement effects. In addition, as a limiting case a perturbation approach to QRE has been presented and its validity conditions have been discussed.     

Effects of magic-angle spinning on spin-lattice relaxations in talc

The spin-lattice relaxation times T₁ of ¹H and ²⁹Si spins in talc have been measured at room temperature with and without magic-angle spinning (MAS) of the sample. Paramagnetic impurities work as relaxation centers. ¹H T₁ depends on the spinning rate, whereas ²⁹Si T₁ is independent of the spinning rate. These facts demonstrate that spin diffusion plays an important role in ¹H relaxation but not in ²⁹Si relaxation. ²⁹Si spins relax through dipole-dipole interactions with electron spins directly, which mechanism is not affected by spinning. The relaxation rates have been analyzed theoretically.     

Multiple quantum spin counting techniques with quadrupolar nuclei

Phase incremented and continuous irradiation multiple spin correlation methods are applied to spin [Formula: see text] nuclei with small quadrupole couplings such as (7)Li in LiCl and are shown to successfully produce a coherently coupled dipolar spin network. Application to the analogous Na salt shows successful spin correlation evolving at a slower rate due to the weaker homonuclear dipolar coupling strength between Na nuclei. The results are analysed using a statistical approach. Spin counting is non-trivial as not only multiple quantum coherences between spins are generated but also within the quadrupolar spin levels. Na(2)C(2)O(4) is investigated as a material with non-negligible quadrupole coupling and it is in this limit that the spin correlation techniques are found to break down.     

Quantum information processing by NMR using a 5-qubit system formed by dipolar coupled spins in an oriented molecule

Quantum information processing by NMR with small number of qubits is well established. Scaling to higher number of qubits is hindered by two major requirements (i) mutual coupling among qubits and (ii) qubit addressability. It has been demonstrated that mutual coupling can be increased by using residual dipolar couplings among spins by orienting the spin system in a liquid crystalline matrix. In such a case, the heteronuclear spins are weakly coupled, but the homonuclear spins often become strongly coupled. In such circumstances, the strongly coupled spins, which yield second order spectra, can no longer be individually treated as qubits. However, it has been demonstrated elsewhere, that the 2(N) energy levels of a strongly coupled N spin-1/2 system can be treated as an N-qubit system. For this purpose the various transitions have to be identified to well defined energy levels. This paper consists of two parts. In the first part, the energy level diagram of a heteronuclear 5-spin system is obtained by using a newly developed heteronuclear z-cosy (HET-Z-COSY) experiment. In the second part, implementation of logic gates, preparation of pseudopure states, creation of entanglement, and entanglement transfer is demonstrated, validating the use of such systems for quantum information processing.     

Distance measurements in spin-1/2 systems by 13C and 31P solid-state NMR in dense dipolar networks

In this article solid-state NMR methods for the determination of internuclear dipole-dipole couplings between homonuclear spin-1/2 nuclei are presented. They are suitable for relatively dense dipolar networks which are still dominated by 2-spin interactions. C-/R-symmetry theory is applied to create a double-quantum average Hamiltonian using phase-modulated radio-frequency irradiation and magic-angle sample-rotation. Symmetry derived pulse sequences with improved compensation against chemical shift anisotropies were found assuming a small isotropic chemical shift difference and using numerical calculations of the spin dynamics. Moreover it is shown that a constant time procedure can be used to acquire reliable double-quantum build-up curves even in systems in which damping obscures oscillations in their symmetric build-up curve. This technique is demonstrated on four crystalline model compounds with 31P and 13C spin systems typical for inorganic and biological applications. Comparison to crystal structure data indicates that the distances derived this way from 31P and 13C double-quantum NMR carry only small systematic errors caused for example by anisotropic J-coupling, dipolar contributions from adjacent spins and relaxation.     

Long-lived states in solution NMR: theoretical examples in three- and four-spin systems

Long-lived spin states have been observed in a variety of systems. Although the dynamics underlying the long lifetimes of these states are well understood in the case of two-spin systems, the corresponding dynamics in systems containing more spins appear to be more complex. Recently it has been shown that a selection rule for transitions mediated by intramolecular dipolar relaxation may play a role in determining the lifetimes of long-lived states in systems containing arbitrary numbers of spins. Here we present a theory of long-lived states in systems containing three and four spins and demonstrate how it can be used to identify states that have little or no intramolecular dipolar relaxation.     

Transverse magnetization transfer under planar mixing conditions in spin systems consisting of three coupled spins 1/2

Polarization transfer under planar mixing conditions is a widely used tool in modern NMR-experiments. In the case of two coupled spins 1/2 or a chain of three or more spins 1/2 with only nearest neighbor couplings, it is only possible to transfer a single magnetization component (longitudinal magnetization in the principle axis system of the planar coupling tensors). However, if all couplings in a three-spin system are non-zero, it turns out that all magnetization components can be efficiently transferred even under strictly planar mixing conditions. In this article a detailed theoretical analysis is presented based on analytical transverse coherence transfer functions and on the underlying commutator algebra. In addition, transverse magnetization transfer is demonstrated experimentally. The results show that in highly coupled spin systems, as for example in the case of partially aligned samples with many residual dipolar couplings, special care has to be taken to avoid phase distortions if planar mixing steps are used.     

Analytical polarization and coherence transfer functions for three dipolar coupled spins 12

Analytical polarization and coherence transfer functions are presented for a spin system consisting of three dipolar coupled homonuclear spins 12 under energy matched conditions. Based on these transfer functions, optimal durations of Hartmann-Hahn mixing periods can be determined for arbitrary dipolar coupling constants D(12), D(13), and D(23). In addition, the dependence of the transfer efficiency on the relative size of the dipolar coupling constants is illustrated.     

Direct conversion of EPR dipolar time evolution data to distance distributions

Shallow electron spin echo envelope modulations due to dipole-dipole couplings between electron spins provide information on the radial distribution function of the spins in disordered systems while angular correlations between spin pairs are negligible. Under these conditions and in the absence of orientational selection, the dipolar time evolution data can be quantitatively simulated for arbitrary radial distribution functions by shell factorization, i.e., by performing the orientational average separately for thin spherical shells and multiplying the signals of all the shells. For distances below 5 nm, a linear superposition of the signals of the shells is sufficient. The dipolar time evolution data can be separated into this linear contribution and a nonlinear background. The linear contribution can then be converted directly to a radial distribution function. For a series of shape-persistent and flexible biradicals with end-to-end distances between 2 and 5 nm, shell factorization and direct conversion of the data are in good agreement with each other and with force-field computations of the end-to-end distances. The neglect of orientation selection does not cause significant distortions of the determined distance distributions.     

Two-dimensional hyperfine sublevel correlation spectroscopy: powder features for S=1/2, I=1

The lineshapes of two-dimensional magnetic resonance spectra of disordered or partially ordered solids are dominated by ridges of singularities in the frequency plane. The positions of these ridges are described by a branch of mathematics known as catastrophe theory concerning the mapping of one 2D surface onto another. We systematically consider the characteristics of HYSCORE spectra for paramagnetic centers having electron spin S=1/2 and nuclear spin I=1 in terms of singularities using an exact solution of the nuclear spin Hamiltonian. The lineshape characteristics are considered for several general cases: zero nuclear quadrupole coupling; isotropic hyperfine but arbitrary nuclear quadrupole couplings; coincident principal axes for the nuclear hyperfine and quadrupole tensors; and the general case of arbitrary nuclear quadrupole and hyperfine tensors. The patterns of singularities in the HYSCORE spectra are described for each case.     

Berry phase of coupled two arbitrary spins in a time-varying magnetic field

In this paper, we investigate the Berry phase of two coupled arbitrary spins driven by a time-varying magnetic field where the Hamiltonian is explicitly time-dependent. Using a technique of time-dependent gauge transform the Berry phase and time-evolution operator are found explicitly in the adiabatic approximation. The general solutions for arbitrary spins are applied to the spin-1/2\ system as an example of explanation.     

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.     

Spinning-frequency-dependent narrowband RF-driven dipolar recoupling

Dipolar recoupling techniques of homonuclear spin pairs are commonly used for distance or orientation measurements in solids. Accurate measurements are interfered with by broadening mechanisms. In this publication narrowband RF-driven dipolar recoupling magnetization exchange experiments are performed as a function of the spinning frequency to reduce the effect of zero-quantum T(2) relaxation. To enhance the exchange of magnetization between the coupled spins, a fixed number of rotor-synchronous pi-pulses are applied at spinning frequencies approaching the rotational resonance (R(2)) conditions. The analysis of the powder averaged dipolar decay curves of the spin magnetizations as a function of the spinning frequency provides a quantitative measure of the dipolar coupling. An effective Hamiltonian for this experiment is derived, taking into account all chemical shift parameters of the spins. The length of the nbRFDR mixing time and the number of rotor cycles per pi-pulse are optimized by numerical simulations for sensitive probing of the dipolar coupling strength. The zero-quantum T(2) relaxation time can easily be taken into account in the data analysis, because the overall exchange time is almost constant in these experiments. Spinning-frequency-dependent nbRFDR experiments near the m = 1 and m = 2 R(2) condition are shown for doubly (13)C-labeled hydroxybutyric acid. Copyright 2000 Academic Press.     

Superposition of scalar and residual dipolar couplings: analytical transfer functions for three spins 1/2 under cylindrical mixing conditions

The superposition of scalar and residual dipolar couplings gives rise to so-called cylindrical mixing Hamiltonians in dipolar coupling spectroscopy. General analytical polarization and coherence transfer functions are presented for three cylindrically coupled spins 12 under energy-matched conditions. In addition, the transfer efficiency is analyzed as a function of the relative coupling constants for characteristic special cases.     

Stimulated polarization wave process in spin 3/2 chains

Stimulated wave of polarization, triggered by a flip of a single spin, presents a simple model of quantum amplification. Recently, it has been demonstrated that, in an idealized one-dimensional Ising spin 1/2 chain with nearest-neighbor interactions and realistic spin 1/2 chain including the natural dipole-dipole interactions, irradiated by a weak resonant transverse field, a wave of flipped spins can be triggered by a single spin flip. Here we focuse on control of polarization wave in chain of spin 3/2, where the nuclear quadrupole interaction is dominant. Results of simulations for 1D spin chains and rings with up to five spins are presented.     

On Heisenberg exchange of high spins

The well-known Kaplan-Alexander equations for chemical exchange are generalized to include Heisenberg exchange of high spins (S > 1/2). General expressions are obtained for the effect of the exchange on the shape and width of lines and on the population of spin eigenstates. The broadening action of an arbitrary spin on a spin of 1/2 is taken as an example.     

Quantum information processing with large nuclear spins in GaAs semiconductors

We propose an implementation for quantum information processing based on coherent manipulations of nuclear spins I=3/2 in GaAs semiconductors. We describe theoretically an NMR method which involves multiphoton transitions and which exploits the nonequidistance of nuclear spin levels due to quadrupolar splittings. Starting from known spin anisotropies we derive effective Hamiltonians in a generalized rotating frame, valid for arbitrary I, which allow us to describe the nonperturbative time evolution of spin states generated by magnetic rf fields. We identify an experimentally observable regime for multiphoton Rabi oscillations. In the nonlinear regime, we find Berry phase interference.