Determination of dipole coupling constants using heteronuclear multiple quantum NMR

The problem of extracting dipole couplings from a system of N spins I = 1/2 and one spin S by NMR techniques is analyzed. The resolution attainable using a variety of single quantum methods is reviewed. The theory of heteronuclear multiple quantum (HMQ) NMR is developed, with particular emphasis being placed on the superior resolution available in HMQ spectra. Several novel pulse sequences are introduced, including a two-step method for the excitation of HMQ coherence. Experiments on partially oriented [1−13C] benzene demonstrate the excitation of the necessary HMQ coherence and illustrate the calculation of relative line intensities. Spectra of high order HMQ coherence under several different effective Hamiltonians achievable by multiple pulse sequences are discussed. A new effective Hamiltonian, scalar heteronuclear recoupled interactions by multiple pulse (SHRIMP), achieved by the simultaneous irradiation of both spin species with the same multiple pulse sequence, is introduced. Experiments are described which allow heteronuclear couplings to be correlated with an S-spin spreading parameter in spectra free of inhomogeneous broadening.

[1]  R. R. Ernst,et al.  Double quantum cross polarization via dipolar order , 1981 .

[2]  A. N. Garroway,et al.  High resolution NMR spectroscopy in solids , 1976 .

[3]  A. Pines,et al.  Double-quantum cross-polarization NMR in solids , 1980 .

[4]  P. Diehl,et al.  The rα structure of [1-13C]benzene by NMR of oriented molecules: A study of the possible precision and of solvent effects , 1979 .

[5]  J. Waugh.  Uncoupling of local field spectra in nuclear magnetic resonance: determination of atomic positions in solids. , 1976, Proceedings of the National Academy of Sciences of the United States of America.

[6]  A. Pines,et al.  Search procedure for optimizing high-order multiple-quantum transition intensities , 1982 .

[7]  Robert W Vaughan,et al.  High-resolution, solid state NMR , 1978 .

[8]  B. L. Neff,et al.  High resolution 13C NMR in solids: 13C local fields of CH, CH2, and CH3 , 1977 .

[9]  J. Ackerman,et al.  Resolved Dipolar Coupling Spectra of Dilute Nuclear Spins in Solids , 1975 .

[10]  Richard R. Ernst,et al.  Selective detection of multiple quantum transitions in NMR by two-dimensional spectroscopy , 1977 .

[11]  Walter I. Goldburg,et al.  Nuclear-Magnetic-Resonance Line Narrowing by a Rotating rf Field , 1965 .

[12]  J. Reimer,et al.  Selective high resolution proton NMR spectra in solids , 1979 .

[13]  R. R. Ernst,et al.  Dipole-coupled carbon-13 spectra, a source of structural information on liquid crystals , 1979 .

[14]  M. E. Stoll,et al.  Explicit demonstration of spinor character for a spin-1/2 nucleus via NMR interferometry. Technical report , 1977 .

[15]  R. R. Ernst,et al.  Double quantum cross polarization. Heteronuclear excitation and detection of NMR double quantum transitions in solids , 1980 .

[16]  Haeberlen Ulrich,et al.  High resolution NMR in solids : selective averaging , 1976 .

[17]  G. Drobny,et al.  Fourier transform multiple quantum nuclear magnetic resonance , 1978 .

[18]  Ad Bax,et al.  Separation of the different orders of NMR multiple-quantum transitions by the use of pulsed field gradients , 1980 .

[19]  J. Ackerman,et al.  Structure determination by dipolar coupling measurements of dilute nuclear spins in a polycrystalline solid , 1975 .

[20]  R. R. Ernst,et al.  Coherence transfer by radiofrequency pulses for heteronuclear detection of multiple-quantum transitions , 1980 .

[21]  S. Vega.  Multiple-quantum cross-polarization NMR on spin systems with I=12 and S=32 in solids , 1981 .

[22]  E. Hahn,et al.  Nuclear Double Resonance in the Rotating Frame , 1962 .

[23]  Warren S. Warren,et al.  Theory of selective excitation of multiple‐quantum transitions , 1980 .

[24]  A. J. Vega,et al.  Double resonance interferometry: relaxation times for dipolar forbidden transitions and off-resonance effects in an AX spin system. Interim report , 1977 .

[25]  R. R. Ernst,et al.  Coherence transfer echoes , 1978 .

[26]  U. Haeberlen,et al.  Coherent Averaging Effects in Magnetic Resonance , 1968 .

[27]  A. Saika,et al.  High‐resolution J‐resolved NMR spectra of dilute spins in solids , 1981 .

[28]  A. J. Vega,et al.  Heteronuclear dipolar modulated chemical shift spectra for geometrical information in polycrystalline solids , 1976 .

[29]  H. Primas,et al.  On the analysis of high-resolution nuclear magnetic resonance spectra: I. Methods of calculating N.M.R. spectra , 1963 .

[30]  Selective proton observed heteronuclear dipolar modulated chemical shift spectra in solids , 1980 .

[31]  L. Mueller.  Sensitivity enhanced detection of weak nuclei using heteronuclear multiple quantum coherence , 1979 .

[32]  G. Bodenhausen,et al.  Multiple quantum spin-echo spectroscopy , 1980 .

[33]  High-resolution NMR spectra in inhomogeneous magnetic fields: application of total spin coherence transfer echoes , 1981 .

[34]  J. Lindon,et al.  NMR Spectroscopy Using Liquid Crystal Solvents , 1975 .