Cd-111 and Cd-113 Spin-Lattice Relaxation in CdMoO4 By Paramagnetic Centers in the Absence of Spin Diffusion

In an ongoing effort to understand the solid-state spin-lattice relaxation mechanism and its modulation for heavy-nuclei spin-1/2 systems like Pb-207 and Tl-203/Tl-205, we have serendipitously observed that the recovery of a saturated Cd-111 (or Cd-113) nuclear magnetization in CdMoO4 shows the three distinct time regions elucidated by Bodart [Phys. Rev. B 54, 15291 (1996)] when nuclear-spin relaxation is dominated by paramagnetic impurity relaxation in the complete absence of nuclear-spin diffusion

(207)Pb Spin-Lattice Relaxation in Solid PbMoO(4) and PbCl(2)

We have measured the (207)Pb nuclear spin-lattice relaxation rate R as a function of temperature T at two nuclear magnetic resonance frequencies omega(0) in the ionic solids lead molybdate (PbMoO(4)) and lead chloride (PbCl(2)). R is unexpectedly large, proportional to T(2), and independent of omega(0). Taken together with previous work in lead nitrate [Pb(NO(3))(2)], these results show that the relaxation does not depend on the nature or rotational motion of the counterion, particularly since the counterion in lead chloride is a single chlorine atom. The theory that explains the observed relaxation rate is reviewed. A second-order Raman process dominates the observed relaxation process. It involves the modulation of the spin-rotation interaction by the lattice vibrations

Spin-Lattice Relaxation of Heavy Spin-1/2 Nuclei in Diamagnetic Solids: A Raman Process Mediated By Spin-Rotation Interaction

We present a theory for the nuclear spin-lattice relaxation of heavy spin-1/2 nuclei in solids, which explains within an order of magnitude the unexpectedly effective lead and thallium nuclear spin-lattice relaxation rates observed in the ionic solids lead molybdate, lead chloride, lead nitrate, thallium nitrate, thallium nitrite, and thallium perchlorate. The observed rates are proportional to the square of the temperature and are independent of magnetic field. This rules out all known mechanisms usually employed to model nuclear spin relaxation in lighter spin-1/2 nuclei. The relaxation is caused by a Raman process involving the interactions between nuclear spins and lattice vibrations via a fluctuating spin-rotation magnetic field. The model places an emphasis on the time dependence of the angular velocity of pairs of adjacent atoms rather than on their angular momentum. Thus the spin-rotation interaction is characterized not in the traditional manner by a spin-rotation constant but by a related physical parameter, the magnetorotation constant, which relates the local magnetic field generated by spin rotation to an angular velocity. Our semiclassical relaxation model involves a frequency-mode description of the spectral density that can directly be related to the mean-square amplitudes and mode densities of lattice vibrations in the Debye model

Spin-Lattice Relaxation of Heavy Spin-1/2 Nuclei in Diamagnetic Solids: A Raman Process Mediated By Spin-Rotation Interaction

We present a theory for the nuclear spin-lattice relaxation of heavy spin-1/2 nuclei in solids, which explains within an order of magnitude the unexpectedly effective lead and thallium nuclear spin-lattice relaxation rates observed in the ionic solids lead molybdate, lead chloride, lead nitrate, thallium nitrate, thallium nitrite, and thallium perchlorate. The observed rates are proportional to the square of the temperature and are independent of magnetic field. This rules out all known mechanisms usually employed to model nuclear spin relaxation in lighter spin-1/2 nuclei. The relaxation is caused by a Raman process involving the interactions between nuclear spins and lattice vibrations via a fluctuating spin-rotation magnetic field. The model places an emphasis on the time dependence of the angular velocity of pairs of adjacent atoms rather than on their angular momentum. Thus the spin-rotation interaction is characterized not in the traditional manner by a spin-rotation constant but by a related physical parameter, the magnetorotation constant, which relates the local magnetic field generated by spin rotation to an angular velocity. Our semiclassical relaxation model involves a frequency-mode description of the spectral density that can directly be related to the mean-square amplitudes and mode densities of lattice vibrations in the Debye model

A combined NMR and DFT study of Narrow Gap Semiconductors: The case of PbTe

In this study we present an alternative approach to separating contributions to the NMR shift originating from the Knight shift and chemical shielding by a combination of experimental solid-state NMR results and ab initio calculations. The chemical and Knight shifts are normally distinguished through detailed studies of the resonance frequency as function of temperature and carrier concentration, followed by extrapolation of the shift to zero carrier concentration. This approach is time-consuming and requires studies of multiple samples. Here, we analyzed $^{207}$Pb and $^{125}$Te NMR spin-lattice relaxation rates and NMR shifts for bulk and nanoscale PbTe. The shifts are compared with calculations of the $^{207}$Pb and $^{125}$Te chemical shift resonances to determine the chemical shift at zero charge carrier concentration. The results are in good agreement with literature values from carrier concentration-dependent studies. The measurements are also compared to literature reports of the $^{207}$Pb and $^{125}$Te Knight shifts of $n$- and $p$-type PbTe semiconductors. The literature data have been converted to the currently accepted shift scale. We also provide possible evidence for the "self-cleaning effect" property of PbTe nanocrystals whereby defects are removed from the core of the particles, while preserving the crystal structure.Comment: 34 pages, 9 figure

(119)Sn Spin-Lattice Relaxation in Alpha-SnF(2)

The temperature and magnetic field dependencies of the (119)Sn nuclear spin-lattice relaxation rate in alpha-SnF(2) indicate the presence of two relaxation mechanisms. At temperatures below 350 K, the relaxation is dominated by a nuclear spin-rotation interaction modulated by lattice vibrations, as has been seen for Pb and Tl salts. This (119)Sn relaxation pathway is less effective in SnF(2) than it is for (207)Pb, (203)Tl, and (205)Tl relaxation in some Pb and Tl salts but it is more effective than (111)Cd and (113)Cd relaxation in some Cd salts. Above 350 K, there is an additional contribution to the observed relaxation rate. The most likely candidate for this thermally activated contribution is the modulation of the (119)Sn-(19)F dipolar interaction by fluoride-ion motion

H-1 Nuclear Magnetic Resonance Spin-Lattice Relaxation, C-13 Magic-Angle-Spinning Nuclear Magnetic Resonance Spectroscopy, Differential Scanning Calorimetry, and X-Ray Diffraction of Two Polymorphs of 2,6-Di-Tert-Butylnaphthalene

Polymorphism, the presence of structurally distinct solid phases of the same chemical species, affords a unique opportunity to evaluate the structural consequences of intermolecular forces. The study of two polymorphs of 2,6-di-tert-butylnaphthalene by single-crystal x-ray diffraction, differential scanning calorimetry (DSC), C-13 magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, and H-1 NMR spin-lattice relaxation provides a picture of the differences in structure and dynamics in these materials. The subtle differences in structure, observed with x-ray diffraction and chemical shifts, strikingly affect the dynamics, as reflected in the relaxation measurements. We analyze the dynamics in terms of both discrete sums and continuous distributions of Poisson processes