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015%). In case of 2H, Eq. 31) is reduced to DnQ ¼ (3=4)(e2 qQ=h)(3 cos2 u À 1): (2:32) This orientation-dependent splitting of peaks yields a clue on how a C2H vector of a molecule under consideration is oriented to the applied magnetic field when single crystalline, mechanically, or magnetically oriented samples are utilized. In many instances, however, most of samples are not always homogeneously oriented with respect to B0, but are randomly distributed as in microcrystalline or powder samples.

For nuclei with 2p electrons such as 13C, 15N, etc. the Brief Outline of NMR Parameters 33 relative chemical shift is predominantly governed by the paramagnetic term, and for the 1H nucleus by the first and third terms. The paramagnetic term is expressed by a function of excitation energy, bond order, and electron density according to the sum-over-state (SOS) method in the simple form as follows:    À h2 e2 4pm2e ÞS r À3 2p ðEm À En ÞÀ1 Q, (3:4) s p ¼ À m0  where Em À En is the singlet–singlet excitation energy of the nth occupied and the mth unoccupied orbitals, and  Qis a factor including the bond order and electron density.

Yamaguchi, M. Tanio, H. Konishi, S. Inoue, A. Naito, R. Needleman, J. K. Lanyi, and H. Saitoˆ, 1999, Biophys. , 76, 1523–1531. [18] S. Yamaguchi, S. Tuzi, M. Tanio, A. Naito, J. K. Lanyi, R. Needleman, and H. Saitoˆ, 2000, J. Biochem. (Tokyo), 127, 861–869. [18a] S. Tuzi, A. Naito, and H. Saitoˆ, 1993, Eur. J. , 218. 837–844. [19] K. Schmidt-Rohr and H. W. Spiess, 1994, Multidimensional Solid-state NMR and Polymers, Academic Press, London. [20] N. Bloembergen and J. A. , 1, 731–746. [21] A. Abragam, 1961, The Principles of Nuclear Magnetism, Claredon Press, Oxford.

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