Anomalous nuclear spin-lattice relaxation in copper small particles

Anomalously long nuclear spin-lattice relaxation time is expected in small metallic particles when the life time width of the conduction electron energy levels is smaller than their mean spacing. A new method for setting nuclear magnetization to zero is developed in order to measure the relaxation time in Cu small particles. The anomaly is observed in the relaxation of⁶³Cu in the particles with the diameters smaller than 100 A at temperatures below 0.5 K.     

Anisotropy of spin-lattice relaxation

The anisotropy is determined for the spin-lattice relaxation time in the presence of a strong magnetic field in crystals of the NaCl type due to the components of a generalized hyperfine-interaction spin-Hamiltonian. It is shown that taking into account components other than the contact, dipole, and quadrupole interactions leads to an additional angular dependence for the relaxation time and also to additional relaxation transitions.     

Carbon-13 spin-lattice relaxation times and nuclear overhauser enhancements in some simple fluorocarbons

Carbon-13 spin-lattice relaxation times (T₁) and ¹³C-{¹⁹F} nuclear Overhauser enhancement (NOE) factors have been measured for some simple fluorocarbons by pulse-Fourier transform methods—‘progressive saturation’ and ‘dynamic Overhauser enhancement’. The NOE factors are shown to be large for ¹³C with directly bonded fluorines, and the values for T₁ and the NOE factors are similar to those obtained elsewhere on the corresponding hydrocarbons.     

Temperature dependence of the spin-lattice relaxation rates in the triplet state of pyrazine at low temperatures

The electron spin-Lattice relaxation, (SLR) rate constants have been measured for the triplet state at pyrazine-d₄ in a cyclohexane matrix from 1 to 8 K by resolving the phosphorescent decay curve into three exponential components. A matrix kinetics is presented that gives the relationship between the SLR rate constants and the observed decay component rate constants and the decay component intensities of the three zero-field levels. An exact numerical procedure based on the Newton-Raphson technique is described in detail for systems of two and three coupled levels. This procedure was used to find the SLR rate constants starting from either the decay component rate constants or the decay component intensities. Both the matrix kinetics and the numerical procedure should be useful in many other studies involving multilevel systems whose sublevels are connected by some combination of SLR and microwaves. The observed SLR rate constants are best explained as a function of temperature as the sum of a direct process (linear in T) and a Raman process (T² dependence). Their relative magnitudes indicate that the Raman process is probably antharmonic. Vancus mechanisms for SLR in this system are examined, and a short review of SLR theory and experiment is given. The nature of the zero-field sublevels in pyrazine-J₄ is also discussed as is the effect of the choice of matrix solvent upon SLR rate constants and the phosphorescent spectrum.     

Proton spin-lattice relaxation study of polymer solutions

Proton spin-lattice relaxation times of solvent molecules were measured on ternary mixtures of a polymer and two solvents by the adiabatic rapid-passage method. The selective adsorption of a good solvent was verified by this experimental technique for the systems benzene—cyclohexane—polystyrene(PS), benzene—carbon tetrachloride—poly(methyl methacrylate)(PMMA), and chloroform—carbon tetrachloride—PMMA. The number of molecules of adsorbed benzene per monomeric unit of PS was estimated to be about four, which is almost identical with that determined previously by thermodynamic measurements. The number of molecules of benzene and chloroform adsorbed on PMMA were also determined to be about five and four, respectively. It was found that the interaction between chloroform and PMMA has the greatest effect on the molecular motion of the solvent, whereas the benzene—PS interaction is weak.     

Probing protein hydration and aging of food materials by the magnetic field dependence of proton spin-lattice relaxation times

Most cheeses can be considered as solid emulsions of milk fat in a matrix of water and proteins. Regions of each of the phases can be liquid during processing and maturation. Identifying these regions and monitoring changes in them is important as a prelude to controlling the structure of the final cheese. We concentrate on the behavior of water in the vicinity of proteins as a function of cheese aging. Our method utilizes nuclear magnetic relaxation dispersion (NMRD) associated with the frequency dependence of water spin-lattice relaxation rates using the field cycling NMR technique. This method provides insight into the dynamical behavior of water molecules on a very large time scale. Moreover, we can distinguish between molecular motion in bulk and motion in the vicinity of a source of relaxation, such as proteins. A fit of our dispersion data using a theory developed by J.-P. Korb and R.G. Bryant (J. Chem. Phys. 115 (2001) 23) allowed us to determine the degree of hydration of proteins as a function of aging. In particular, we find that protein hydration increases with ripening.     

Temperature dependence of the nitrogen-14 nuclear quadrupole resonance frequencies in selected triazine compounds

Symmetric-1,3,5 triazine compounds are heterocyclic ring molecules containing three nitrogen atoms at the 1,3,5 sites. Because of their inherent high symmetry and the existence of a large number of compounds with different chemical groups attached to the ring, this class of compounds is ideally suited to NQR studies. We are reporting measurements of T^★₂ and the temperature dependence of the frequencies for a number of the nitrogen-14 NQR lines in trichloromelamine, cyanuric acid, trichloroisocyanuric acid, cyanuric chloride, and melamine. The results of these measurements yielded T^★₂'s for cyanuric chloride almost an order of magnitude larger than for the other compounds. The variations of the frequencies with temperature appear to be consistent with the Bayer—Kushida model.     

Anomalous temperature dependence of nuclear quadrupole interactions in strongly hydrogen-bonded systems from first principles

We present an analysis of the effect of finite temperatures on the deuteron nuclear quadrupole coupling constants in a strongly hydrogen-bonded molecular crystal by means of first-principles Car-Parrinello molecular-dynamics simulations. Our findings agree well with experiments and provide a microscopic explanation of the anomalous increase of the quadrupole coupling in this class of systems. We show that a simple model based on the anharmonicity of the hydrogen bond potential fails to describe the temperature dependence of the couplings even qualitatively. Instead, the inclusion of fluctuations and disorder in terms of atomic motion of the surrounding molecules turns out to be important to obtain the correct magnitude of the temperature effect.     

Proton spin-lattice relaxation studies. N-aryl-1-isoindolinones

Proton spin-lattice relaxation rates (R₁ values) have been measured, at 270 MHz, for a series of N-aryl isoindolinones. A normalization procedure has been used to enable comparison of R₁ values in different compounds by minimizing the effects on relaxation rates of changes in motional correlation times accompanying changes in substitution patterns. A substantial (4.3-fold) dynamic range of R₁ values has been observed, and individual values have been correlated with the molecular environments of the nuclei. There is evidence for an interring relaxation process.     

Electric-field-induced changes in spin-lattice relaxation in polar liquids

Spin—lattice relaxation times of acetonitrile, aligned by an electric field, have been measured. In contrast to earlier investigations on other polar liquids, no electric-field effects on T₁ could be established. The apparent discrepancy is discussed in terms of electric conduction and inhomogeneity of the applied electric field.     

Effects of lattice anharmonicity on spin-lattice relaxation in solids

A derivation is given for the formulas defining the operator for the spin-lattice interaction as averaged over the orbital motion of the unpaired electron in the solid. Simple formulas are derived for the constants of the spin-lattice interaction. It is shown that the relaxation time T₁ of this interaction may be substantially dependent on the concentration of lattice defects at helium temperatures; approximate relations between T₁ and the phonon mean free path are derived.     

Multireference CI calculation of nuclear quadrupole coupling constants of CN+ and CN-: rovibrational dependence

The 14N quadrupole coupling constants of rovibrational levels of the X1sigma+ and c1sigma+ states of CN+, and the ground electronic state of CN- are calculated from molecular wavefunctions which explicitly describe nuclear displacement. From the electronic states considered, the excited 1sigma+ state of CN is predicted to exhibit the strongest N coupling, at least in the ground vibrational state. Compared to the vibrational dependence of the 14N QCC's, which is found to be significant in all cases, the rotational dependence is predicted to be unimportant. Special attention is paid to the assessment of adequacy of the expectation value approach to the evaluation of the electric field gradient tensor within the applied multireference configuration interaction formalism. Spectroscopic constants are derived from corresponding potential energy curves to testify to the quality of the correlated wave functions used.     

Water proton spin-lattice relaxation behaviour in heterogeneous biological systems

The water proton spin-lattice relaxation rate has been measured for a condensed 50% deuterated erythrocyte water system. Nuclear relaxation data, obtained in non-selective and selective modes, indicate that cross relaxation between erythrocyte and water protons occurs. The observed selective relaxation enhancement is interpreted in terms of intermolecular nuclear interactions modulated by motions which satisfy the ω_oT_c > 1 condition. Selective relaxation rates are here proposed to be more sensitive to interface characteristics than the non-selective ones.