Overall and internal motions of substituted benzenes studied by means of selective proton magnetic longitudinal relaxation time measurements

Selective T ₁ measurements at different temperatures on seven substituted benzenes in CDCl₃ solution show that for these molecules the rotational diffusion model applies. Anisotropic reorientation is important if the molecules contain two polar substituents para to each other. Anomalies in the temperature dependence of the T ₁ values in a 2-methyl substituted phenol are explained by intermolecular hydrogen bonds, which strongly influence the molecular motion. In a 2,6-dimethyl substituted phenol this effect is absent. The correlation times and the energy barriers for methyl rotation of methyl and methoxy groups are determined. The reorientation of methoxy groups around the aryl oxygen bond is slower than the molecular motion. The T ₁ values of ring protons and substituents can in some cases be used for spectral assignment. Expressions are given for the T ₁ value of a ring proton relaxed by an ortho methyl or methoxy group and for the T ₁ value of a reorienting methoxy group in the case of dipolar relaxation and axially symmetric behaviour of the molecule.     

Molecular reorientations of 1-bromo- and 1-iodo-adamantanes 1H N.M.R. relaxation study

Second moments and spin-lattice relaxation times, T ₁ and T _1ρ, have been measured from 100 K to 400 K for the protons in powdered 1-bromo and 1-iodo-adamantanes. Analysis of these data have shown that the reorientations are uniaxial in the low temperature phases. In the high temperature disordered phase of bromo-adamantane, the reorientation is endospherical and a slow molecular translational motion also exists. In the high temperature disordered phase of iodo-adamantane the reorientation is 12-fold uniaxial, in agreement with the Incoherent Quasi-elastic Neutron Scattering (I.Q.N.S.) experiments. All the results correspond to the crystallographic structures deduced from X-ray scattering.     

Proton magnetic relaxation and molecular motion in polycrystalline amino acids

A proton magnetic resonance and relaxation study has been carried out on seven polycrystalline amino acids from 130 to 500 K at 60·2 MHz. These amino acids contain no methyl groups and all exhibit a single relaxation minimum. The measurements are well accounted for by the Kubo-Tomita theory of relaxation assuming a single correlation time which follows a simple activation law. In all cases the source of relaxation is provided by reorientation of the -NH₃ groups in the zwitterion form of the molecules; other protons are relaxed by spin-exchange with those of the -NH₃ group. The measured relaxation constants are consistent with inter-proton distances in the -NH₃ groups recently measured by neutron diffraction.     

Proton magnetic relaxation and molecular motion in polycrystalline amino acids

A proton magnetic relaxation study has been carried out on a further seven polycrystalline amino acids from 130 to 500 K at 60·2 MHz, supplemented by measurements of the spectrum down to 4 K on five of them. These amino acids all have one or two methyl groups in their side chain, and exhibit two relaxation minima. Clear evidence is given that the relaxation minima at lower temperatures are attributable to reorientation of the methyl groups, while those at higher temperatures are attributable to reorientation of the -NH₃ groups in the zwitterion configuration of the molecules. Values of the relaxation constants, activation energies and time factors which best characterize the kinetics of both motions are tabulated. Effects of methyl group tunnelling are found for methionine and valine.     

Interferometric measurements of the dipole polarizability α of molecules between 300 K and 1100 K

The temperature dependence of the dipole polarizability α(λ, T) of free atoms and molecules is determined by precise measurements of the refractive index n of gases in the extended temperature range between 300 K and 1100 K for wavelength λ = 632·99 nm, using a specially constructed Michelson twin interferometer. α of the noble gases is observed to be independent of T. α of the molecular gases H₂, N₂, O₂, and CH₄ increases with increasing temperature by an amount of approximately 1 per cent per 1000 K. These results are in excellent agreement with theoretical predictions. They will be compared to previously measured temperature dependent polarizabilities.     

Proton diffusion in the room-temperature phase of [(NH4)1−xRbx]3H(SO4)2 as studied by 1H spin-lattice relaxation in the rotating frame

Proton diffusion in the room-temperature phase (phase II) of [(NH₄)_1?xRb_x]₃H(SO₄)₂ (0≤x≤1) has been studied by means of ¹H spin-lattice relaxation times in the rotating frame, T_1ρ. The ¹H T_1ρ values were measured at 200.13 MHz in the range of 380–490 K. The ammonium protons and the acidic protons have independent T_1ρ values in the higher temperature range of phase II, suggesting that the spin diffusion between the two species is ineffective. The translational diffusion of the acidic protons is the most dominant mechanism to relax both the ammonium protons and the acidic protons in phase II. The ¹H T_1ρ values in phase II are analyzed theoretically and the motional parameters are obtained. The results of NMR well explain the macroscopic proton conductivity.     

N.M.R. study of solid perfluorocyclobutane

spin-lattice relaxation times and linewidth measurements for fluorine nuclei in solid perfluorocyclobutane are presented. The results are discussed in terms of D _2d molecular species performing fast internal motion. The relaxation measurements corroborate the existance of four solid-solid phase transitions and give some insight into their nature. The activation energies for molecular reorientation and self-diffusion processes are found to be 28·0 and 32·2 kJ mol^-1, respectively.     

NMR investigations of hexamethyldisilane confined in controlled pore glasses: Pore size distribution and molecular dynamics studies

In this work, the melting-point depression and molecular dynamics of hexamethyldisilane confined within five controlled pore glasses, with mean diameters ranging from 7.9 to 23.9 nm, are studied by high-field (9.4 T) nuclear magnetic resonance (NMR), and the results are discussed with reference to the bulk substance. The melting-point depression in pores with radiusR follows the simplified Gibbs-Thompson equation ΔT=k _p/(R−s) with ak _p value of 74 K · nm and ans value of 1 nm. To our knowledge, this is the first time thek _p value of hexamethyldisilane is reported. Proton spin-lattice relaxation times (T ₁), spin-spin relaxation times (T ₂), and diffusivities (D) are reported as a function of temperature. The confinement in the pores gives rise to substantial changes in the molecular dynamics and the phase behavior. The line-shape measurements reveal a two-phase system assigned to a relatively mobile component at the pore walls and a crystalline solid at the center of the pores. However, theT ₂ measurements show that the mobile phase also embraces a minor component attributed to nonfrozen liquid in pockets or micropores. The diffusivity of the major narrow-line component is approximately three orders of magnitude larger than that in the plastic bulk phase, reflecting fast diffusion of mobile molecules. Below the melting region,T ₁ of the narrow line is significantly shorter thanT ₁ of the broad line, suggesting that the molecular reorientation is more hindered close to the surface than at the center of the pore.     

Proton N.M.R. study of the dynamics of the ammonium ion in ferroelectric langbeinite, (NH4)2Cd2(SO4)3

The proton N.M.R. lineshape of polycrystalline Langbeinite, (NH₄)₂Cd₂(SO₄)₃, has been studied in the temperature range 300 K to 1·8 K. The resonance line is motionally narrowed over the entire temperature range, and the low temperature proton line shows clear evidence for tunnelling motion of the ammonium ion between spin-symmetry states. From a computer simulation of the lineshape, we obtain an estimate for the tunnelling splitting parameter, J, of the torsional ground state of the ammonium ion, as 375 ± 125 gauss. For an undistorted tetrahedral crystal field this corresponds to a tunnelling splitting Δ = 4J = 6·3 ± 2·1 MHz.

Pulsed proton N.M.R. studies have also been carried out on the above compound at 30·8 MHz and 48·2 MHz and the spin-lattice relaxation time (T ₁) has been measured by the π - t - π/2 pulse sequence as a function of temperature down to 77 K. At 30·8 MHz, a T ₁ minimum of 13 ms occurs at 105·8 K, and is ascribed to random reorientations of the NH₄ ⁺ ion. An activational energy barrier of 0·74 ± 0·1 kcal/mole and an associated pre-exponential factor of 8·0 × 10^-13 s are calculated for the above motional process, and the value of the activation energy is correlated with the tunnelling splitting of the torsional ground state.

An anomaly in T ₁ has been observed at the ferroelectric Curie point (95 K), indicating the order-disorder nature of the transition. This is the first experimental evidence relating to the nature of the transition in Langbeinite.     

Phase transition and proton exchange in 1,3-diazinium hydrogen chloranilate monohydrate

In the hydrate crystal of 1:1 salt with 1,3-diazine and chloranilic acid (H₂ca), (1,3-diazineH)·H₂O·Hca, an unique hydrogen-bonded molecular aggregate is formed. There exists proton disorder in the N–H...O hydrogen bond between 1,3-diazinium ion and water (H₂O) of crystallization. In order to reveal dynamic aspect of this disorder, ³⁵Cl NQR measurements were conducted. Two resonance lines observed at 35.973 and 35.449 MHz at 321 K split into four lines below T _c?=?198 K clearly showing occurrence of a solid–solid phase transition; 36.565, 36.357, 36.011, 35.974 MHz at 77 K. Temperature dependence of spin-lattice relaxation time T ₁ in high-temperature phase was observed to obey an Arrhenius-type relation with the activation energy of 8.5 kJ mol^???1. This result leads to the conclusion that proton exchange in the N–H...O hydrogen bond takes place in the high-temperature phase. Specific heat measurements by DSC resulted in the transition entropy ΔS?=?1.3 J K^???1 per 1 mole [(1,3-diazineH)·H₂O·Hca]₂ which is far less than 2R ln2 = 11.5 J K^???1 mol^???1. It is expected that proton exchange in the two hydrogen bonds within the aggregate does not occur independently but concertedly with strong correlation in the high-temperature phase.     

A nuclear magnetic resonance study of molecular motion in solid diethylamine and in diethylamine clathrate deuterate

The proton magnetic resonance second moment and spin-lattice relaxation data are reported for the two solids namely pure diethylamine and diethylamine clathrate deuterate, over the temperature range 77 K to 270 K. The results indicate that in both materials the only motion which occurs at a rate great enough to affect the N.M.R. observables is methyl group reorientation and for such motion activation energies of (2·9₀±0·02) kcal mole^-1 and (2·3₄±0·02) kcal mole^-1 are obtained for pure diethylamine, and the deuterate, respectively. The strength of the dipolar interaction in the deuterate as estimated from both the second moment and the maximum in the temperature dependence of nuclear relaxation rate is consistent with a carbon-proton distance of 1·10 Å and a large degree of chemical exchange of the amine protons with the deuterons of D₂O.     

NMR Study of proton transport in crystalline antimonic acid

Pulsed ¹H NMR measurements are reported for polycrystalline antimonic acid (Sb₂O₅·nH₂O) in the temperature range 145 K<T<330 K at 60 MHz. Motional narrowing occurs at T>220 K and the relaxation behaviour is compatible with fast proton transport with a distribution of activation energies.     

35Cl N.M.R. relaxation in aqueous sodium perchlorate solutions

The relaxation time, T _1ρ, for ³⁵Cl in perchlorate ion in aqueous solutions is found to be 0·25 s. T _1ρ is insensitive to the presence of most first row transition metals; however, a weak complex with manganous ion is demonstrated, and the perchlorate ion-manganous exchange rate is shown to be between 3 × 10⁴ s^-1 and 3·6 × 10⁷ s^-1. In the absence of manganous ion, the relaxation is dominated by the nuclear electric quadrupole interaction; however, a dipolar contribution is observed with manganous ion present.     

Molecular dynamics in comb-like ionene as studied by NMR

Proton and fluorine second moment and spin-lattice relaxation timesT ₁ andT _lρ have been employed to study molecular dynamics in the comb-like I-6,6-16-Me-BF₄ ionene in the temperature range from 110 up to 300 K. The existence of motions of methyl groups, trans-gauche isomerization, and/or rotation of the main- and side-chain méthylene groups, as well as isotropic reorientation of tetrafluoroborate ions were established. The observed relaxation behaviors are explained by motional models which assume Davidson-Cole asymmetrical distribution of correlation times. The best-fit motional parameters are given.     

Molecular motion in liquid benzene by nuclear magnetic resonance

The proton spin-lattice relaxation time, T ₁, has been measured for a series of mixtures of benzene in perdeuterobenzene for the liquid in equilibrium with its vapour over the temperature range from below the normal freezing point up to the critical temperature. The two contributions to T ₁ due to interactions within the molecule (T _{1 intra}) and between molecules (T _{1 inter}) have been separated and are found to be very different in magnitude and in variation with temperature. The variation and magnitude of T _{1 inter} correlates well with other translational motion dependent properties such as self diffusion and viscosity. The correlation of T _{1 intra} with other re-orientation dependent properties such as deuteron T ₁ and Rayleigh scattering is poor.

The observed variation in T _{1 intra} and in particular the broad maximum at higher temperatures is then interpreted as due to a combination of dipolar and spin-rotation effects. This interpretation results in good agreement between the activation energies for re-orientational molecular motion deduced from proton T ₁ and deuteron T ₁. It supports the Hubbard theory for the relation between the dipolar and spin-rotation correlation times τ_d and τ_sr. It gives a rough value, 3·8 kc/s, for the spin-rotation interaction constant for protons in benzene. Reasonable values for τ_d and τ_sr are predicted and for all temperatures τ_sr < τ_d as expected.

There is clearly a considerable difference between the re-orientational and translational motion of the molecules in liquid benzene but the exact nature of the difference cannot be elucidated.     

Study of ionic motion in salts of the type (NH4)2MX6 by NMR relaxation

The proton spin-lattice relaxation time in the laboratory frame, T₁, and rotating frame T_1ρ for polycrystalline cubic (NH₄)₂SiF₆, (NH₄)₂SnBr₆ and (NH₄)₂SnCl₆ have been measured over a temperature range 60–500°K. Reorientation of the ammonium ion is generally the dominant relaxation mechanism and T₁ minima are observed in all samples. Activation energies are low in each case, being 2·2 Kcal/mole for the fluosilicate, 1·44 and 1·24 Kcal/mole for the bromo- and chloro-stannate respectively. For the bromostannate a λ-point occurs at 145°K above which the activation energy apparently decreases to 0·26 Kcal/mole. Anion reorientation is detected in the fluosilicate at high temperatures, the correlation time for this motion being obtained from T_1ρ measurements. There is also some evidence to suggest anion reorientation is becoming important in the stannihalides at high temperatures. The proton T_1ρ in the stannibromide is largely determined by the rapid quadrupolar controlled relaxation of the bromine nuclei. Values for the bromine T₁ are deduced and the quadrupolar relaxation mechanism discussed.     

Proton relaxation studies of 17α hydroxy- and 21 hydroxy-progesterones by1H NMR

Proton spin-lattice relaxation timesT ₁ in 17α hydroxy- and 21 hydroxy-progesterones have been performed in the temperature range from 100 to 400 K at the frequencies of 30 and 90 MHz. The dynamic processes involving the methyl group reorientation about the threefold symmetry axis of the C−C bond are separated, and their activation parameters are determined.     

The properties of liquid nitrogen

Measurements are reported of the nitrogen-nucleus spin-lattice relaxation time, T ₁, in liquid nitrogen ¹⁴N₂ and liquid nitrogen ¹⁵N₂ along the liquid-vapour coexistence line from 77·3 K up to the critical temperature and for the fluid at the critical density up to 145 K. Values of the molecular reorientational correlation time, τ _Q , and the molecular angular momentum correlation time, τ _sr , are determined. The values of τ _Q and τ _sr and the relation between them are discussed in terms of various theories of molecular reorientation in molecular liquids. The values of τ _Q and τ _sr are also compared with those predicted by computer simulation methods. It is concluded that the molecular reorientation in liquid nitrogen is not by classical reorientational diffusion except possibly at temperatures near the triple point. It is suggested that at higher temperatures the reorientation is on average by rather large angles and that the process may be quantum mechanical to some extent. (For paper I in this series see reference [8].)     

Nuclear magnetic relaxation by self-diffusion in solid lithium:T 1-frequency dependence

We report on measurements of the⁷Li nuclear spin relaxation timeT ₁ in solid lithium as a function of temperature (?170°C≦T≦+180°C) and Larmor frequency (450kHz≦v _Li≦31.5 MHz). Using a relaxation model developed by Wolf and Cavelius and combining it with Seeger's diffusion formalism, the diffusion parameters for mono-and divacancy migration were evaluated by a least squares fit to the newly obtainedT ₁ data as well as to previousT _1? measurements. The result for the self-diffusion coefficientD ^SD is given byD ^SD=D ₁₀·exp(?Q ₁/RT)·[1+D ₂₁·exp(?Q ₂₁/RT)], withD ₁₀=0.038 cm²s^?1,Q ₁=12.0 kcal mol^?1,D ₂₁=250,Q ₂₁=4 kcal mol^?1 andR=1.98₅·10^?3 kcal mol^?1 degree^?1. Due to the flexibility of Seeger's formula, which contrasts with the standard Arrhenius interpretation of diffusion, discrepancies between earlier high- and low-frequency NMR investigations were eliminated. Furthermore, an excellent agreement with available results from tracer experiments was achieved by taking into account the theoretical predictions of the isotope effect and the vacancy correlation factor.