Multiple Quantum NMR Dynamics Research Articles

Multiple Quantum NMR in One-Dimensional and Nano-Scale Systems: Theory and Computer Simulations

We investigate several exactly solvable models of multiple quantum (MQ) NMR dynamics. We study MQ NMR dynamics of one-dimensional systems (chains and rings) and nano-voids filled with spin-carrying atoms or molecules in a strong external magnetic field. Our focus is the problem of the profile of MQ NMR coherences (i.e., the dependence of the intensities of MQ NMR coherences on their orders). We find that integrable one-dimensional systems exhibit peculiar behavior that does not shed much light on a more generic situation. On the other hand, important lessons can be extracted from our solution for the nano-scale systems. We find that the profile of the intensities of the MQ NMR coherences is rather exponential than Gaussian as was proposed earlier. We also address the cluster growth in the course of the evolution of MQ NMR coherences.

MQ NMR dynamics in dipolar ordered state at negative temperature

We investigate theoretically the Multiple Quantum (MQ) NMR dynamics at negative absolute temperatures in systems of nuclear spins 1/2 coupled by the dipole–dipole interactions and with the initial conditions determined by the dipolar ordered state. Two different methods of MQ NMR are used. One of them is based on the measurement of the dipolar energy. The other method uses an additional resonance (π/4)y-pulse after the preparation period of the standard MQ NMR experiment. It is shown that at negative temperatures many-spin clusters and spin correlations are created faster, and the intensities of MQ coherences are higher than in the usual MQ NMR experiments. So, the eighth-order MQ coherence in 10-spin system of the cyclopentane molecule appears to be 1.5 times faster and its intensity is four orders higher than at positive temperatures. The proposed MQ NMR methods at negative absolute temperatures can be used for the investigation of many-spin dynamics of nuclear spins in solids.

Low temperature MQ NMR dynamics in dipolar ordered state

We investigate analytically and numerically the Multiple Quantum (MQ) NMR dynamics in dipolar ordered spin systems of nuclear spins 1/2 at low temperatures. We consider two different methods of MQ NMR. One of them is based on the measurement of the dipolar energy. The other method uses an additional resonance (π/4)y-pulse after the preparation period of the standard MQ NMR experiment in solids and allows one to measure the Zeeman energy. Both considered methods are sensitive to the contribution of remote spins in the interaction and to the spin system structure. The QS method is sensitive to the spin number in the molecule while the PS method gives very similar time dependencies of the intensities of MQ coherences for different spin numbers. It is shown that the use of the dipolar ordered initial state has the advantage of exciting the highest order MQ coherences in clusters of 4m identical spins, where m=1,2,3,…, that is impossible to do with the standard MQ method. MQ NMR methods based on the dipolar ordered initial states at low temperatures complement the standard NMR spectroscopy for better studying structures and dynamic processes in solids.

Multiple quantum NMR dynamics in a gas of spin-carrying molecules in fluctuating nanopores

The effect of Gaussian fluctuations of nanopores filled with a gas of spin-carrying molecules ( s = 1/2) on the multiple quantum (MQ) NMR dynamics is investigated at different variances and correlation times of the fluctuations. We show that the fluctuations smooth out the evolution of MQ NMR coherence intensities which rapidly oscillate as functions of time in the absence of fluctuations. The growth and decay of the MQ coherence clusters in the fluctuating nanopore are also investigated.

The multiple quantum NMR dynamics in systems of equivalent spins with a dipolar ordered initial state

The multiple quantum (MQ) NMR dynamics in the system of equivalent spins with the dipolar ordered initial state is considered. The high symmetry of the MQ Hamiltonian is used in order to develop the analytical and numerical methods for an investigation of the MQ NMR dynamics in the systems consisting of hundreds of spins from "the first principles". We obtain the dependence of the intensities of the MQ NMR coherences on their orders (profiles of the MQ NMR coherences) for the systems of $200 - 600$ spins. It is shown that these profiles may be well approximated by the exponential distribution functions. We also compare the MQ NMR dynamics in the systems of equivalent spins having two different initial states, namely the dipolar ordered state and the thermal equilibrium state in the strong external magnetic field.

Multiple quantum NMR of spin-carrying molecules in nanopores: high order corrections to the two-spin/two-quantum Hamiltonian

This paper is devoted to multiple quantum (MQ) NMR spectroscopy in nanopores filled by a gas of spin-carrying molecules (s = 1/2) in a strong external magnetic field. It turns out that the high symmetry of the spin system in nanopores yields a possibility to overcome the problem of the exponential growth of the Hilbert space dimension with an increase in the number of spins and to investigate MQ NMR dynamics in systems consisting of several hundred spins. We investigate the dependence of the MQ coherence intensities on their order (the profile of the MQ coherence intensities) for a spin system governed by the standard MQ NMR Hamiltonian (the nonsecular two-spin/two-quantum Hamiltonian) together with the second order correction of average Hamiltonian theory. It is shown that the profile depends on the value of this correction and varies from an exponential to a logarithmic one.

Multiple quantum NMR dynamics of spin-12 carrying molecules of a gas in nanopores

We consider the multiple quantum (MQ) NMR dynamics of a gas of spin carrying molecules in nanocavities. MQ NMR dynamics is determined by the residual dipole-dipole interactions, which are not averaged completely due to the molecular diffusion in nanopores. Since the averaged nonsecular Hamiltonian describing MQ NMR dynamics depends on only one coupling constant, this Hamiltonian commutes with the square of the total spin angular momentum Î2. We use the basis of common eigenstates of Î2 and the projection of I on the external magnetic field for investigation of MQ NMR dynamics. This approach allows us to study MQ NMR dynamics in systems consisting of several hundreds of spins. The analytical approximation of the stationary profile of MQ coherences is obtained. The analytical expressions for MQ NMR coherence intensities of the five-spin system in a nanopore are found. Numerical investigations allow us to find the dependencies of intensities of MQ coherences on their orders (the profiles of MQ coherences) in systems consisting of 600 spins and even more. It is shown that the stationary MQ coherence profile in the considered system is an exponential one.

Multiple quantum NMR dynamics in dipolar ordered spin systems

We investigate analytically and numerically the multiple-quantum (MQ) NMR dynamics in systems of nuclear spins $1∕2$ coupled by the dipole-dipole interactions in the case of the dipolar ordered initial state. We suggest two different methods of MQ NMR. One of them is based on the measurement of the dipolar temperature in the quasiequilibrium state which is established after the time of order ${\ensuremath{\omega}}_{\mathit{loc}}^{\ensuremath{-}1}$ (${\ensuremath{\omega}}_{\mathit{loc}}$ is the dipolar local field) after the MQ NMR experiment. The other method uses an additional resonance ${(\ensuremath{\pi}∕4)}_{y}$ pulse after the preparation period of the standard MQ NMR experiment in solids. Many-spin clusters and correlations are created faster in such experiments than in the usual MQ NMR experiments and can be used for the investigation of many-spin dynamics of nuclear spins in solids.

Dipolar temperature and multiple-quantum NMR dynamics in dipolar ordered-spin systems

We investigate analytically and numerically the multiple-quantum (MQ) NMR dynamics in systems of nuclear spins 1/2 coupled by dipole-dipole interactions in the case of the dipolar-ordered initial state. We suggest a new method of MQ NMR based on the measurement of the dipolar temperature in the quasi-equilibrium state, which establishes after the time of order ωloc−1 (ωloc is the dipolar local field) after the MQ NMR experiment. Manyspin clusters and correlations are created faster in such an experiment than in usual MQ NMR experiments and can be used for the investigation of the many-spin dynamics of nuclear spins in solids.

Exact results on spin dynamics and multiple quantum NMR dynamics in alternating spin-1/2 chains with XY Hamiltonian at high temperatures

We extend the picture of a transfer of nuclear spin-1/2 polarization along a homogeneous one-dimensional chain with the XY-Hamiltonian to the inhomogeneous chain with alternating nearest neighbour couplings and alternating Larmor frequencies. To this end, we calculate exactly the spectrum of the spin-1/2 XY-Hamiltonian of the alternating chain with an odd number of sites. The exact spectrum of the XY-Hamiltonian is also applied to study the multiple quantum (MQ) NMR dynamics of the alternating spin-1/2 chain. MQ NMR spectra are shown to have the MQ coherences of zero and $\pm$ second orders just as in the case of a homogeneous chain. The intensities of the MQ coherences are calculated.

Line shapes of multiple quantum NMR coherences in one-dimensional quantum spin chains in solids

General formulae for intensities of multiple quantum (MQ) NMR coherences in systems of nuclear spins coupled by the dipole–dipole interactions are derived. The second moments of the MQ coherences of zero- and second orders are calculated for infinite linear chains in the approximation of the nearest neighbor interactions. Supercomputer simulations of intensities of MQ coherences of linear chains are performed at different times of preparation and evolution periods of MQ NMR experiments. The second moments obtained from the developed theory are compared with the results of the supercomputer analysis of MQ NMR dynamics. The linewidth information in MQ NMR experiments is discussed.

Supercomputer analysis of one-dimensional multiple-quantum dynamics of nuclear spins in solids

We report the results of supercomputer simulations of multiple-quantum (MQ) NMR dynamics of linear nuclear spin chains of 12–15 spins coupled by the dipole–dipole interactions (DDI). The supercomputer simulations demonstrate that MQ dynamics of linear spin chains exhibits oscillatory behavior. MQ coherence growth in powders of non-interacting linear spin chains is also investigated. We compare the results of the supercomputer simulations in single-crystals and powders with the predictions of a phenomenological Gaussian approximation and the experimental data for MQ NMR dynamics in quasi-one-dimensional spin clusters in apatites.

Multiple-quantum NMR dynamics in the quasi-one-dimensional distribution of protons in hydroxyapatite

Multiple-quantum NMR dynamics are reported for the quasi-one-dimensional distribution of uniformly spaced proton spins in hydroxyapatite, Ca 5(OH)(PO 4) 3, using a phase-incremented even-order selective time-reversal pulse sequence. The initial increase of the effective size N with the preparation time for creation of multiple-quantum coherences is linear, in qualitative (but not quantitative) agreement with calculations based upon an “incremental shell” model recently developed by Levy and Gleason. An upward curvature observed at longer preparation times is qualitatively ascribed to the incomplete isolation of the linear chains. Slight deficiencies of hydroxyl groups in the linear chain lead to a measurable decrease in the slope of the linear portion of the curve.