Spin rotations

The muon spin relaxation technique uses the implantation and subsequent decay of muons, n+, in matter. The muon has a polarized spin of 1/2 [22]. When implanted, the muons interact with the local magnetic field and decay (lifetime = 2.2 ps) by emitting a positron preferentially in the direction of polarization. Adequately positioned detectors are then used to determine the asymmetry of this decay as a function of time, A t). This function is thus dependant on the distribution of internal magnetic fields within a 

134 5 Experimental Aspects of Lanthanide Single-Molecule Magnet Physics 

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Spin-rotation 1 Reorientation and time dependence of angular momentum Small molecules only [M... 

McClung RED 1996 Spin-rotation relaxation theory Encyclopedia of Nuclear Magnetic Resonance ed D M Grant and R K Harris (Chichester Wiley) pp 4530-5... 

N-protonation the absolute magnitude of the Ad values is larger than for Af-methylation <770MR(9)53>. Nuclear relaxation rates of and have been measured as a function of temperature for neat liquid pyridazine, and nuclear Overhauser enhancement has been used to separate the dipolar and spin rotational contributions to relaxation. Dipolar relaxation rates have been combined with quadrupole relaxation rates to determine rotational correlation times for motion about each principal molecular axis (78MI21200). NMR analysis has been used to determine the structure of phenyllithium-pyridazine adducts and of the corresponding dihydropyridazines obtained by hydrolysis of the adducts <78RTC116>. 

Hubbard P. S. Theory of nuclear magnetic relaxation by spin-rotational interactions in liquids. Phys. Rev. 131, 1155-65 (1963). 

Courtney J. A., Armstrong R. L. A nuclear spin relaxation study of the spin-rotation interaction in spherical top molecules. Can. J. Phys. 50, 1252-61 (1972). 

Suvernev A. A., Temkin S. I. Spin-rotational NMR-relaxation of spherical molecules in gas phase, Chem. Phys. Lett. 154, 49-55 (1989). 

OIDEP usually results from Tq-S mixing in radical pairs, although T i-S mixing has also been considered (Atkins et al., 1971, 1973). The time development of electron-spin state populations is a function of the electron Zeeman interaction, the electron-nuclear hyperfine interaction, the electron-electron exchange interaction, together with spin-rotational and orientation dependent terms (Pedersen and Freed, 1972). Electron spin lattice relaxation Ti = 10 to 10 sec) is normally slower than the polarizing process. 

The process of spin-lattice relaxation involves the transfer of magnetization between the magnetic nuclei (spins) and their environment (the lattice). The rate at which this transfer of energy occurs is the spin-lattice relaxation-rate (/ , in s ). The inverse of this quantity is the spin-lattice relaxation-time (Ti, in s), which is the experimentally determinable parameter. In principle, this energy interchange can be mediated by several different mechanisms, including dipole-dipole interactions, chemical-shift anisotropy, and spin-rotation interactions. For protons, as will be seen later, the dominant relaxation-mechanism for energy transfer is usually the intramolecular dipole-dipole interaction. 

When other relaxation mechanisms are involved, such as chemical-shift anisotropy or spin-rotation interactions, they cannot be separated by application of the foregoing relaxation theory. Then, the full density-matrix formalism should be employed. 

QUANTUM MONODROMY AND MOLECULAR SPECTROSCOPY A. Spin-Rotation Coupling... 

The simplest example of angular momentum coupling is provided by the scaled spin-rotation coupling Hamiltonian... 

A model which takes into account the spin-rotation interaction has been found to satisfactorily explain the 0 rotation band of PHg. The millimetre-wave spectra of HCP and DCP have been compared with those of HCN and DCN. A method of estimating frequencies of bands in this region due to processes such as pseudorotation has been suggested. This new approach involves calculation of the rovibronic energy levels from the effects of quantum-mechanical tunnelling. ... 

For liquids, the dominant relaxation mechanism is the nuclear-nuclear dipole interaction, in which simple motion of one nucleus with respect to the other is the most common source of relaxation [12, 27]. In the gas phase, however, the physical mechanism of relaxation is often quite different. For gases such as the ones listed above, the dominant mechanism is the spin-rotation interaction, in which molecular collisions alter the rotational state of the molecule, leading to rotation-induced magnetic fluctuations that cause relaxation [27]. The equation governing spin-rotation relaxation is given by... 

The first possibility is that the attractive potential associated with the solid surface leads to an increased gaseous molecular number density and molecular velocity. The resulting increase in both gas-gas and gas-wall collision frequencies increases the T1. The second possibility is that although the measurements were obtained at a temperature significantly above the critical temperature of the bulk CF4 gas, it is possible that gas molecules are adsorbed onto the surface of the silica. The surface relaxation is expected to be very slow compared with spin-rotation interactions in the gas phase. We can therefore account for the effect of adsorption by assuming that relaxation effectively stops while the gas molecules adhere to the wall, which will then act to increase the relaxation time by the fraction of molecules on the surface. Both models are in accord with a measurable increase in density above that of the bulk gas. 

Whereas in CF4 we can ignore the surface relaxation term, this term is significant for c-C4F8 at 291 K, with the relative weighting becoming increasingly important as we add additional molecular layers, as shown below. This is equivalent to Eq. (3.5.6), with the bulk fluid term set to the spin-rotation relaxation of the bulk gas. It is clear that in such a system, in comparison with CF4 at 294 K, the effect of liquid phase surface relaxation cannot be ignored. 

R. Y. Dong, M. Bloom 1970, (Determination of spin-rotation constants in flu-orinated methane molecules by means of nuclear spin relaxation measurements), Can. J. Phys. 48, 793. 

Live oil with dissolved methane does not follow the above correlations as methane relaxes by a spin-rotation mechanism, even when dissolved in liquid hydrocarbons [13]. The Ti relaxation time as a function of rj/T is illustrated in Figure 3.6.2 for different gas/oil ratios expressed in units of m3 m-3 as a parameter. The solid line is the fit for zero gas/oil ratio and is given by Eq. (1). 

The relaxation of gaseous methane, ethane and propane is by the spin-rotation mechanism and each pure component can be correlated with density and temperature [15]. However, the relaxation rate is also a function of the collision cross section of each component and this must be taken into account for mixtures [16]. This is in contrast to the liquid hydrocarbons and their mixtures that relax by dipole-dipole interactions and thus correlate with the viscosity/temperature ratio. 

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