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Title: Nuclear magnetic relaxation in [sup 13]CH[sub 2] and [sup 13]CH[sub 3] coupled spin systems and variable angle spinning lineshape analysis for quadrupolar nuclei with half integer spins

Miscellaneous ·
OSTI ID:6960435

The carbon-13 multiplet spin-lattice relaxation in [sup 13]CH[sub 2] and [sup 13]CH[sub 3] spin systems is studied in detail by various nonselective and selective pulse techniques. Simultaneous fitting of the resulting relaxation curves with various rates and initial conditions allows for the extraction of both auto- and cross-correlated dipolar spectral densities which can provide detailed information on the molecular anisotropic reorientation. In addition, the [sup 13]CH[sub 3] coupled spin relaxation can characterize the methyl internal rotation dynamics. The cross-correlation between the dipolar and chemical shift anisotropy (CSA) interactions is found to be appreciable. Dipolar-CSA cross-correlated spectral densities introduce relaxation pathways that couple together magnetization modes with different spin inversion symmetries. Consideration of the dipolar-CSA cross-correlated spectral densities not only improves the accuracy of the measurement of dipolar spectral densities but also allows for the determination of the dipolar-CSA cross-correlated spectral densities themselves, providing a new measure of the anisotropy of the shielding tensor. NMR spectroscopy of quadrupolar nuclei in solids generally yields broad lines even when magic angle spinning is applied. Broadening of the central transition of quadrupolar nuclei with half integer spins is caused by the anisotropy of the second order quadrupolar interaction. A straightforward approach is presented that combines average Hamiltonian theory and a numerical solution of a classical banded matrix describing the equation of motion for a quadrupolar nucleus under variable angle sample spinning conditions. At either of two fourth rank magic angles, a simple three parameter lineshape is obtained, and the three breakpoints are related directly to the quadrupolar constant and its asymmetry parameter.

Research Organization:
Utah State Univ., Logan, UT (United States)
OSTI ID:
6960435
Resource Relation:
Other Information: Thesis (Ph.D)
Country of Publication:
United States
Language:
English