Spin lattice relaxation temperature

D.E. Woessner B.S. Snowden, Jr. (1967). J. Chem. Phys., 47, 378-381. Proton spin-lattice relaxation temperature dependence in ammonium bromide. 

If the amount of the sample is sufficient, then the carbon skeleton is best traced out from the two-dimensional INADEQUATE experiment. If the absolute configuration of particular C atoms is needed, the empirical applications of diastereotopism and chiral shift reagents are useful (Section 2.4). Anisotropic and ring current effects supply information about conformation and aromaticity (Section 2.5), and pH effects can indicate the site of protonation (problem 24). Temperature-dependent NMR spectra and C spin-lattice relaxation times (Section 2.6) provide insight into molecular dynamics (problems 13 and 14). 

The measurement of correlation times in molten salts and ionic liquids has recently been reviewed [11] (for more recent references refer to Carper et al. [12]). We have measured the spin-lattice relaxation rates l/Tj and nuclear Overhauser factors p in temperature ranges in and outside the extreme narrowing region for the neat ionic liquid [BMIM][PFg], in order to observe the temperature dependence of the spectral density. Subsequently, the models for the description of the reorientation-al dynamics introduced in the theoretical section (Section 4.5.3) were fitted to the experimental relaxation data. The nuclei of the aliphatic chains can be assumed to relax only through the dipolar mechanism. This is in contrast to the aromatic nuclei, which can also relax to some extent through the chemical-shift anisotropy mechanism. The latter mechanism has to be taken into account to fit the models to the experimental relaxation data (cf [1] or [3] for more details). Preliminary results are shown in Figures 4.5-1 and 4.5-2, together with the curves for the fitted functions. 

Fig. 19. Experimental spin alignment decay curves of chain deuterated PS-d3 at temperatures above and below the glass transition for various evolution times t,. Note the different timescales of t2 at the different temperatures. The straight lines indicate the decays of the plateau values on the timescale of the spin-lattice relaxation time T,. Sample characterization Mw = 141000, Mw/Mn = 1.13, atactic...

Experimental data on nitrogen obtained from spin-lattice relaxation time (Ti) in [71] also show that tj is monotonically reduced with condensation. Furthermore, when a gas turns into a liquid or when a liquid changes to the solid state, no breaks occur (Fig. 1.17). The change in density within the temperature interval under analysis is also shown in Fig. 1.17 for comparison. It cannot be ruled out that condensation of the medium results in increase in rotational relaxation rate primarily due to decrease in free volume. In the rigid sphere model used in [72] for nitrogen, this phenomenon is taken into account by introducing the factor g(ri) into the angular momentum relaxation rate... 

The spin-lattice relaxation rate of Chromatium vinosum HIPIP was measured between 5 and 50 K (103). In comparison with the [4Fe-4S] cluster of B. stearothermophilus ferredoxin, the relaxation was found to be faster below 15 K and slower above this temperature. 

Often the electronic spin states are not stationary with respect to the Mossbauer time scale but fluctuate and show transitions due to coupling to the vibrational states of the chemical environment (the lattice vibrations or phonons). The rate l/Tj of this spin-lattice relaxation depends among other variables on temperature and energy splitting (see also Appendix H). Alternatively, spin transitions can be caused by spin-spin interactions with rates 1/T2 that depend on the distance between the paramagnetic centers. In densely packed solids of inorganic compounds or concentrated solutions, the spin-spin relaxation may dominate the total spin relaxation 1/r = l/Ti + 1/+2 [104]. Whenever the relaxation time is comparable to the nuclear Larmor frequency S)A/h) or the rate of the nuclear decay ( 10 s ), the stationary solutions above do not apply and a dynamic model has to be invoked... 

In paramagnetic materials, the relaxation frequency is in general determined by contributions from both spin-lattice relaxation and spin-spin relaxation. Spin-lattice relaxation processes can conveniently be studied in samples with low concentrations of paramagnetic ions because this results in slow spin-spin relaxation. Spin-spin relaxation processes can be investigated at low temperatures where the spin-lattice relaxation is negligible. Paramagnetic relaxation processes have... 

As discussed in Sect. 6.2, the electronic states of a paramagnetic ion are determined by the spin Hamiltonian, (6.1). At finite temperamres, the crystal field is modulated because of thermal oscillations of the ligands. This results in spin-lattice relaxation, i.e. transitions between the electronic eigenstates induced by interactions between the ionic spin and the phonons [10, 11, 31, 32]. The spin-lattice relaxation frequency increases with increasing temperature because of the temperature dependence of the population of the phonon states. For high-spin Fe ", the coupling between the spin and the lattice is weak because of the spherical symmetry of the ground state. This... 

The temperature mapping method used in Ref. [8] is based on measurements of the spin-lattice relaxation time Ti of a suitable liquid such as ethylene glycol filling... 

Fig. 3.5.1 Spin-lattice relaxation data for (a) CF4 and (b) c-C4F8 gas as a function of pressure. The solid curve is the model prediction. Data for CF4 were measured at 181, 294 and 362 K. Small temperature variations were measured for each data point, and were...

SFC-NMR is available from 200 to 800 MHz, and is suitable for all common NMR-detected nuclei. SFC/SFE-NMR requires dedicated probe-heads for high pressure (up to 350 bar) and elevated temperature (up to 100 °C). SFC-NMR is carried out with conventional packed columns, using modifier, pressure and temperature gradients. The resolution of 1H NMR spectra obtained in SFE-NMR and SFC-NMR coupling under continuous-flow conditions approaches that of conventionally recorded NMR spectra. However, due to the supercritical measuring conditions, the 111 spin-lattice relaxation times 7) are doubled. 

It appears that purification of commercially available solvents is sometimes required for the complete elimination of impurity resonances. Occasionally, these impurities may be turned into advantage, as in the case of C2D2CI4 where the (known) C2DHCI4 content may be used as an internal standard for quantitation. Thus, removal of every impurity peak is not always essential for identification and quantitative analysis of stabilisers in PE. Determination of the concentration of additives in a polymer sample can also be accomplished by incorporation of an internal NMR standard to the dissolution prepared for analysis. The internal standard (preferably aromatic) should be stable at the temperature of the NMR experiment, and could be any high-boiling compound which does not generate conflicting NMR resonances, and for which the proton spin-lattice relaxation times are known. 1,3,5-Trichlorobenzene meets the requirements for an internal NMR standard [48]. The concentration should be comparable to that of the analytes to be determined. 

Carotenoids incorporated in metal-substituted MCM-41 represent systems that contain a rapidly relaxing metal ion and a slowly relaxing organic radical. For distance determination, the effect of a rapidly relaxing framework Ti3+ ion on spin-lattice relaxation time,and phase memory time, Tu, of a slowly relaxing carotenoid radical was measured as a function of temperature in both siliceous and Ti-substituted MCM-41. It was found that the TM and 7) are shorter for carotenoids embedded in Ti-MCM-41 than those in siliceous MCM-41. 

Longitudinal relaxation (T ) Recovery of magnetisation along the z axis. The energy lost manifests itself as an infinitesimal rise in temperature of the solution. This used to be called spin-lattice relaxation, a term which originated from solid-state NMR. 

T3C n.m.r. spectra were recorded for the oils produced at 400°, 450°, 550° and 600°C. As the temperature increased the aromatic carbon bands became much more intense compared to the aliphatic carbon bands (see Figure 8). Quantitative estimation of the peak areas was not attempted due to the effect of variations in spin-lattice relaxation times and nuclear Overhauser enhancement with different carbon atoms. Superimposed on the aliphatic carbon bands were sharp lines at 14, 23, 32, 29, and 29.5 ppm, which are due to the a, 8, y, 6, and e-carbons of long aliphatic chains (15). As the temperature increases, these lines... 

The "decrease of the spin temperature means an increase of population difference between the upper and lower energy spin states and consequently an increased sensitivity of the NMR experiment. From Equation (25), the temperature of dilute spins has been lowered by a factor 7x/y1 h, that is, V4 when X = 13C. This means an increased sensitivity of the FID resonance experiment equal to about 4 for the 13C nuclei. Because the X signal is created from the magnetization of dilute nuclei, the repetition time of NMR experiment depends on the spin-lattice relaxation time of the abundant spin species, protons, which is usually much shorter than the spin-lattice relaxation times of the dilute nuclei. This, a further advantage of cross polarization, delay between two scans can be very short, even in the order of few tens of milliseconds. 

In metalloproteins, the paramagnet is an inseparable part of the native biomacromolecule, and so anisotropy in the metal EPR is not averaged away in aqueous solution at ambient temperatures. This opens the way to study metalloprotein EPR under conditions that would seem to approach those of the physiology of the cell more closely than when using frozen aqueous solutions. Still the number of papers describing metalloprotein bioEPR studies in the frozen state by far outnumbers studies in the liquid state. Several additional theoretical and practical problems are related to the latter (1) increased spin-lattice relaxation rate, (2) (bio)chemical reactivity, (3) unfavorable Boltzmann distributions, (4) limited tumbling rates, and (5) undefined g-strain. 

Gayda, J.-P., Bertrand, P., Deville, A., More, C., Roger, G., Gibson, J.F., and Cammack, R. 1979. Temperature dependence of the electronic spin-lattic relaxation time in a 2-iron-2-sulfur protein. Biochimica et Biophysica Acta 581 15-26. 

In the theory of deuteron spin-lattice relaxation we apply a simple model to describe the relaxation of the magnetizations T and (A+E), for symmetry species of four coupled deuterons in CD4 free rotators. Expressions are derived for their direct relaxation rate via the intra and external quadrupole couplings. The jump motion between the equilibrium positions averages the relaxation rate within the same symmetry species. Spin conversion transitions couple the relaxation of T and (A+E). This mixing is included in the calculations by reapplying the simple model under somewhat different conditions. The results compare favorably with the experimental data for the zeolites HY, NaA and NaMordenite [6] and NaY presented here. Incoherent tunnelling is believed to dominate the relaxation process at lowest temperatures as soon as CD4 molecules become localized. 

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