Intermolecular multiple-quantum coherence NMR signals modulated by double distant dipolar fields

A modified CRAZED pulse sequence was applied to obtain the intermolecular multiple-quantum coherence NMR signals from double distant dipolar fields in highly polarized spin systems. Complete theoretical analyses were explicitly derived from the dipolar field treatment combined with product operator formalism. Two typical samples containing several different components were chosen for the experimental verifications. The computer simulations and experimental observations are consistent with the theoretical predictions. The results presented herein provide a convenient way to understand the combined effects of multiple distant dipolar fields from the different components in complicated chemical or biological solutions. When experimental conditions such as selective radio-frequency pulses are not optimal, it may be helpful to identify possible unexpected signals or artefacts of high-resolution NMR spectroscopy in inhomogeneous fields.     

Quantum Treatment of Intermolecular Multiple-Quantum Coherences with IntramolecularJCoupling in Solution NMR

A recently introduced density matrix picture for dipolar effects in solution NMR (1996,J. Chem. Phys.105,874) gave complete solutions for intermolecular multiple-quantum coherences for single-component samples without scalar couplings. This paper, for the first time, shows that this quantum picture can lead to explicit signal expressions for multicomponent samples of molecules with internal scalar couplings (here assumed to generate a first-order spectrum) and long-range dipolar couplings. Experimental observation of a triplet in the indirectly detected dimension for a heteronuclear CRAZED sequence (¹³CHCl₃sample, ZQ or 2Q coherences) gives clear evidence that the coupling is due to the intermolecular dipolar coupling. We also make comparisons with classical pictures which introduce the dipolar demagnetization field in multicomponent spin systems.     

Spin-selective multiple quantum excitation: relative signs of the couplings and ambiguous situations

Homonuclear higher quantum NMR spectra of heteronuclear spin systems result in fewer transitions aiding the analyses. In such experiments the spin states of the heteronuclei do not get disturbed in both single and multiple quantum dimensions resulting in the separation of active homonuclear and passive heteronuclear couplings in two dimensions. The cross sections of the single-quantum dimension get displaced according to the strengths of the passive couplings. The directions of the displacement of these cross sections provide relative signs among the passive couplings. The present study demonstrates the situations when the displacement vectors, though provide the relative signs, could be ambiguous. The dynamics of the spin systems in homo- and heteronuclear multiple quantum studies have been discussed using polarization operator approach. The experimental results on ¹³C- and ¹⁵N-labeled isotopomers of acetonitrile, in both isotropic and thermotropic liquid crystalline phases, are reported.     

SPROM – an efficient program for NMR/MRI simulations of inter- and intra-molecular multiple quantum coherences

A software package has been designed to simulate nuclear magnetic resonance spectra and images. Combining the product operator matrix with the non-linear Bloch equations, the software can efficiently simulate classical and quantum effects including scalar coupling, dipolar coupling, translational diffusion, chemical shift, radiation damping, transverse relaxation, and longitudinal relaxation. One of the most unique features of the software is its ability to incorporate effects of inter- and intra-molecular multiple quantum coherences in complex multiple-spin coupled systems, which are difficult with other existing software packages. The software, written in Visual C++, has a friendly graphical user interface and is easy to use. To cite this article: C. Cai et al., C. R. Physique 9 (2008).     

Anomalous Rotational Resonance Spectra in Magic-Angle Spinning NMR

Magic-angle spinning NMR spectra of samples containing dilute spin-1/2 pairs display broadenings or splittings when a rotational resonance condition is satisfied, meaning that a small integer multiple of the spinning frequency matches the difference in the two isotropic shift frequencies. We show experimental rotational resonance NMR spectra of a 13C2-labeled retinal which are in qualitative disagreement with existing theory. We propose an explanation of these anomalous rotational spectra involving residual heteronuclear couplings between the 13C nuclei and the neighboring 1H nuclei. These couplings strongly influence the rotational resonance 13C spectrum, despite the presence of a strong radiofrequency decoupling field at the 1H Larmor frequency. We model the residual heteronuclear couplings by differential transverse relaxation of the 13C single-quantum coherences. We present a superoperator theory of the phenomenon and describe a numerical algorithm for rapid Liouville space simulations in periodic systems. Good agreement with experimental results is obtained by using a biexponential transverse relaxation model for each spin site.     

Field-dependent nuclear relaxation of spins 1/2 induced by dipole-dipole couplings to quadrupole spins: LaF3 crystals as an example

A general theory of spin-lattice nuclear relaxation of spins I=1/2 caused by dipole-dipole couplings to quadrupole spins S1, characterized by a non-zero averaged (static) quadrupole coupling, is presented. In multispin systems containing quadrupolar and dipolar nuclei, transitions of spins 1/2 leading to their relaxation are associated through dipole-dipole couplings with certain transitions of quadrupole spins. The averaged quadrupole coupling attributes to the energy level structure of the quadrupole spin and influences in this manner relaxation processes of the spin 1/2. Typically, quadrupole spins exhibit also a complex multiexponential relaxation sensed by the dipolar spin as an additional modulation of the mutual dipole-dipole coupling. The proposed model includes both effects and is valid for an arbitrary magnetic field and an arbitrary quadrupole spin quantum number. The theory is applied to interpret fluorine relaxation profiles in LaF3 ionic crystals. The obtained results are compared with predictions of the 'classical' Solomon relaxation theory.     

液体多脉冲及二维FT-NMR实验的乘积算符描述的计算机模拟

本文报道了利用乘积算符方法分析多脉冲及二维FT-NMR实验的模拟程序PROPER-MT.该程序对分析弱耦合I_mS_n(I=1/2;S=(1)/2;1 ≤ m十n<4)自旋体系实验脉冲序列是普遍适用的;它可给出实验过程中体系任何时刻算符的解析表达式.用PROPER-MT程序对一些典型的多脉冲及二维FT-NMR实验进行了模拟,特别对多量子滤波及多自旋滤波脉冲序列进行了分析计算,得到了预期的结果.     

Stochastic dipolar recoupling in nuclear magnetic resonance of solids

I describe a nuclear magnetic resonance (NMR) technique, called stochastic dipolar recoupling (SDR), that permits continuous experimental control of the character of spin dynamics between coherent and incoherent limits in a system of magnetic dipole-coupled nuclei. In the fully incoherent limit of SDR, spin polarization transfers occur at distance-dependent rates without the quantum mechanical interferences among pairwise dipole-dipole couplings that often limit the feasibility or precision of structural studies of solids by NMR. In addition to facilitating structural studies, SDR represents a possible route to experimental studies of effects of decoherence on the dynamics of quantum many-body systems.     

NQR Spin Diffusion in an Inhomogeneous Internal Field

The theory of NQR spin diffusion is extended to the case of spin lattice relaxation and spin diffusion in an inhomogeneous field. Two coupled equations describing the mutual relaxation and the spin diffusion of the nuclear magnetization and dipolar energy were obtained by using the method of nonequilibrium state operator. The equations were solved for short and long times approximation corresponding to the direct and diffusion relaxation regimes.     

Hadamard products of product operators and the design of gradient-diffusion experiments for simulating decoherence by NMR spectroscopy

An extension of the product operator formalism of NMR is introduced, which uses the Hadamard matrix product to describe many simple spin 1/2 relaxation processes. The utility of this formalism is illustrated by deriving NMR gradient-diffusion experiments to simulate several decoherence models of interest in quantum information processing, along with their Lindblad and Kraus representations.