Acetone mobility in zeolite cages with new features in the deuteron NMR spectra and relaxation.

We studied deuteron NMR spectra and spin-lattice relaxation of deuterated acetone-d6, adsorbed into zeolites NaX (1.3) and NaY(2.4) at 100% coverage of sodium cations. At temperatures roughly below 160 K the deuterons are localized and their NMR characteristics are determined by CD3 rotation and rotational oscillations of acetone molecules. In NaX the CD3 rotation and rotational oscillations about the twofold axis of acetone dominate the spectra below 100 K, while above it oscillations also about other axes become important. In NaY dominant features are related to methyl tunnelling and to a smaller extent to rigid acetones, before the rotational oscillations about twofold axis start to prevail above 40 K. The analysis of the strongly non-exponential magnetization recovery was done by applying the recently introduced method (Ylinen et al., 2015 [12]), improved here to take into account the limited fast recovery at the level crossings, 10% at ωt=ω0 and 28% at ωt=2ω0. At first the experimental recovery is fitted by three exponentials with adjustable weights and decay rates. Then these quantities are calculated from activation energy distributions and known expressions for the deuteron relaxation rate. In NaY two distinctly separate activation energy distributions were needed, the dominant one being very broad. The use of three distributions, two of them covering practically the same energies as the broad one, lead to a somewhat better agreement with experiment. In general the theoretical results agree with experiment within experimental scatter. As the final result the mean activation energies and widths are obtained for activation energy distributions.

The effect of a broad activation energy distribution on deuteron spin-lattice relaxation.

Deuteron NMR spectra and spin-lattice relaxation were studied experimentally in zeolite NaY(2.4) samples containing 100% or 200% of CD3OH or CD3OD molecules of the total coverage of Na atoms in the temperature range 20-150K. The activation energies describing the methyl and hydroxyl motions show broad distributions. The relaxation data were interpreted by improving a recent model (Stoch et al., 2013 [16]) in which the nonexponential relaxation curves are at first described by a sum of three exponentials with adjustable relaxation rates and weights. Then a broad distribution of activation energies (the mean activation energy A0 and the width σ) was assumed for each essentially different methyl and hydroxyl position. The correlation times were calculated from the Arrhenius equation (containing the pre-exponential factor τ0), individual relaxation rates computed and classified into three classes, and finally initial relaxation rates and weights for each class formed. These were compared with experimental data, motional parameters changed slightly and new improved rates and weights for each class calculated, etc. This method was improved by deriving for the deuterons of the A and E species methyl groups relaxation rates, which depend explicitly on the tunnel frequency ωt. The temperature dependence of ωt and of the low-temperature correlation time were obtained by using the solutions of the Mathieu equation for a threefold potential. These dependencies were included in the simulations and as the result sets of A0, σ and τ0 obtained, which describe the methyl and hydroxyl motions in different positions in zeolite.

Water confinement in faujasite cages: a deuteron NMR investigation in a wide temperature range. 1. Low temperature spectra.

Deuteron NMR spectra were measured for D2O confined in NaX, NaY, and DY faujasites with various D2O loadings at temperatures ranging from T = 70 K to T = 200 K with the aim to study the molecular mobility of confined water as a function of Si/Al ratio and loading. The recorded spectra were fitted with linear combinations of representative spectral components. At low loading, with the number of water molecules per unit cell close to the abundance of sodium cations, a component related to π-jumps of water deuterons about the 2-fold symmetry axis dominated. For loadings at levels 3 times and 5 times higher than the initial loading level, Pake dublets due to rigid water deuterons dominated the recorded spectra. A set of the quadrupole coupling constant values of localized water deuterons was derived from the analysis of the Pake dublets. Their values were attributed to deuteron positions corresponding to the locations at oxygen atoms in the faujasite framework and locations within hydrogen-bonded water clusters inside faujasite cages. The contributions of the different spectral components were observed to change with increasing temperature according to the Arrhenius law with a characteristic dynamic crossover point at T = 165 K. Below T = 165 K a spectral component was observed whose contribution changed with temperature, yielding the activation energy of about 2 kJ/mol, characteristic for jumps between inversion-related water positions in clusters.

Water confinement in faujasite cages: a deuteron NMR investigation in a wide temperature range. 2. Spectra and relaxation at high temperature.

Deuteron NMR spectra and spin-lattice relaxation were measured for D2O confined in NaX, NaY, and DY faujasites with various loadings at temperatures ranging from 200 to 310 K with the aim to study molecular mobility of confined water. Hysteresis of spin-lattice relaxation was observed for both DY and NaY(2.4) samples at 500% loading (280 water molecules per unit cell) in a heating-cooling cycle between 264.5 and 277.7 K. The hysteresis is most likely reflecting formation and decomposition of water clusters at different temperature. Spin-lattice relaxation rates obtained from the experiment are consistent with a picture of the fast magnetization exchange between two dynamically different deuteron populations. The observed relaxation behavior as a function of temperature and loading is most likely an effect of interplay between translational and rotational diffusion. Translational diffusion of water molecules is found to be related to the strength of the electrostatic interaction of water oxygen atoms to faujasite sodium cations, whereas water molecule reorientations seem to depend on the strength of hydrogen bonding to faujasite oxygen atoms and the strength of hydrogen bonds between water molecules, at outer and inner positions in water clusters, respectively.

Deuteron spin-lattice relaxation in the presence of an activation energy distribution: application to methanols in zeolite NaX.

A new method is introduced for analyzing deuteron spin-lattice relaxation in molecular systems with a broad distribution of activation energies and correlation times. In such samples the magnetization recovery is strongly non-exponential but can be fitted quite accurately by three exponentials. The considered system may consist of molecular groups with different mobility. For each group a Gaussian distribution of the activation energy is introduced. By assuming for every subsystem three parameters: the mean activation energy E(0), the distribution width σ and the pre-exponential factor τ(0) for the Arrhenius equation defining the correlation time, the relaxation rate is calculated for every part of the distribution. Experiment-based limiting values allow the grouping of the rates into three classes. For each class the relaxation rate and weight is calculated and compared with experiment. The parameters E(0), σ and τ(0) are determined iteratively by repeating the whole cycle many times. The temperature dependence of the deuteron relaxation was observed in three samples containing CD(3)OH (200% and 100% loading) and CD(3)OD (200%) in NaX zeolite and analyzed by the described method between 20K and 170K. The obtained parameters, equal for all the three samples, characterize the methyl and hydroxyl mobilities of the methanol molecules at two different locations.

Translational and rotational mobility of methanol-d4 molecules in NaX and NaY zeolite cages: a deuteron NMR investigation.

Nuclear magnetic resonance (NMR) provides means to investigate molecular dynamics at every state of matter. Features characteristic for the gas phase, liquid-like layers and immobilized methanol-d(4) molecules in NaX and NaY zeolites were observed in the temperature range from 300 K down to 20K. The NMR spectra at low temperature are consistent with the model in which molecules are bonded at two positions: horizontal (methanol oxygen bonded to sodium cation) and vertical (hydrogen bonding of hydroxyl deuteron to zeolite framework oxygen). Narrow lines were observed at high temperature indicating an isotropic reorientation of a fraction of molecules. Deuteron spin-lattice relaxation gives evidence for the formation of trimers, based on observation of different relaxation rates for methyl and hydroxyl deuterons undergoing isotropic reorientation. Internal rotation of methyl groups and fixed positions of hydrogen bonded hydroxyl deuterons in methyl trimers provide relaxation rates observed experimentally. A change in the slope of the temperature dependence of both relaxation rates indicates a transition from the relaxation dominated by translational motion to prevailing contribution of reorientation. Trimers undergoing isotropic reorientation disintegrate and separate molecules become localized on adsorption centers at 166.7 K and 153.8K for NaX and NaY, respectively, as indicated by extreme broadening of deuteron NMR spectra. Molecules at vertical position remain localized up to high temperatures. That indicates the dominating role of the hydrogen bonding. Mobility of single molecules was observed for lower loading (86 molecules/uc) in NaX. A direct transition from translation to localization was observed at 190 K.

Dynamics of hydroxyl deuterons and bonded water molecules in NaDY(0.8) zeolite as studied by means of deuteron NMR spectroscopy and relaxation.

Deuteron spin-lattice relaxation and spectra were measured for NaDY (0.8) zeolite containing some heavy water. Two subsystems of deuterons with different mobility were disclosed at low temperatures with their respective relaxation rates differing by two orders of magnitude. Spectra exhibit different shapes related directly to a specific motional model. Hydroxyl deuterons perform incoherent tunneling along the hydrogen bond, then on increasing temperature jumps to excited states and over the barrier appear. Hydrogen bonded water molecules perform 180 degrees rotational jumps about the twofold symmetry axis. Spectral amplitudes are consistent with the water content of 13 D(2)O molecules per unit cell. Above about 240K translational mobility becomes significant and finally water molecules diffuse across the free space of cages. Diversity in temperature dependence of hydroxyl deuteron dynamics may indicate location of adsorbed molecules.

Deuteron NMR spectra and relaxation in fully and partly deuterated (NH4)2ZnCl4.

Deuteron NMR spectra and relaxation were studied at the resonance frequency of 46MHz in polycrystalline fully and partly deuterated (NH(4))(2)ZnCl(4) between 300 and 5K. Spectral components confirm existence of ammonium positions with different potential symmetry, resulting in two- and threefold reorientation of ammonium ions. The temperature dependence of the spin-lattice relaxation rate discloses two time constants in the whole range. The fitting procedure allows the separation into contributions from subsystems of ions in respective potentials. Two relaxation rate maxima are attributed to ions performing threefold uniaxial reorientation at low temperatures. The lower-temperature maximum is observed at T36K. With increasing temperature reorientations about remaining axes start to contribute leading to the other maximum near 100K. The other category of ammonium ions gives rise to the maximum at about 50K. Below this temperature the dominant motion seems to be 180( composite function) reorientations about one twofold axis according to observed spectra. Consistent picture of ion mobility is accomplished for 5%, 30%, 70% and 100% deuterated compounds.

Deuteron spin-lattice relaxation in partly and fully deuterated (NH(4))(2)PdCl(6).

Deuteron spin-lattice relaxation and spectra were studied in partially and fully deuterated (NH(4))(2)PdCl(6) in the temperature range 5-300K. The relaxation rate maximum was observed at 45K in (ND(4))(2)PdCl(6). Its value is reduced due to limited jumps by about 33% relative to the theoretical value expected for threefold reorientations. Limited jumps correspond to an N-D vector jumping between six directions on a cone around a Pd-N vector, the angle between the N-D and Pd-N vectors being denoted Delta. This motion makes a part of the quadrupole interaction ineffective in relaxation thus reducing the maximum rate at 45K. The observed reduction leads to the value Delta=21( composite function). Limited jumps are quenched to a large extent at the order-disorder phase transition and consequently a decrease is observed in the rate. Below the transition ND(4)(+) ions reorient between the tetrahedral orientations of the ordered phase, therefore the quadrupole interaction has the full relaxing efficiency. In the 10% deuterated sample the temperature of the rate maximum is shifted to 35K and below 20K the rate itself is one order of magnitude larger than in (ND(4))(2)PdCl(6). The increase is related to (1) the absence of the order-disorder phase transition and (2) to the enhanced mobility of NH(3)D(+) because of its electric dipole moment. Limited jumps are claimed to be the dominant relaxation mechanism below 20K. The relaxation in the disordered 30% deuterated sample is quite similar to that in 10% sample. The 50% and 70% deuterated samples undergo a transition to the ordered phase. The relaxation is biexponential with the characteristic rates somewhat smaller than those in (ND(4))(2)PdCl(6), but approaching them with increasing deuteration. This variation can be explained with different mobilities and varying relative numbers of the various isotopomers NH(4-n)D(n)(+), n=1-4.

Deuteron NMR relaxation, spectra, and evidence for the order-disorder phase transition in (ND4)2PtCl6.

Deuteron NMR relaxation and spectra were studied at the resonance frequency of 46 MHz in polycrystalline (ND(4))(2)PtCl(6) between 300-5 K. The relaxation rate maximum near 50 K is about 53% smaller than the calculated maximum related to 120 degrees rotations about the threefold symmetry axes of the ammonium ion. The difference is explained by assuming for a N-D vector a total of 24 equilibrium directions, which in groups of six deviate from the nearest Pt-N vector by a certain angle Theta. So-called limited jumps between the directions of each group take place much more frequently than the large-angle rotations, thus rendering a fraction of the deuteron quadrupole coupling ineffective in relaxation. A motional model is presented, which takes into account both these motions simultaneously. A comparison with experimental data leads to Theta=26.0 degrees , in reasonable agreement with earlier neutron diffraction data. A sharp decrease found in the relaxation rate at the order-disorder phase transition temperature of 27.2 K is related to the fact that one of the six equilibrium directions becomes preferred. This leads to a formation of ordered domains, in which the active motion driving the relaxation is 120 degrees rotations. Two components in the spectra found below 55 K are related to domains (broad) and transition regions between domains (narrow). Reasons for the nonexponentiality observed below 20 K are discussed, the most likely explanation being that limited jumps dominate within transition regions and make the corresponding deuterons relax faster than those in domains.

Translation and reorientation of CD4 molecules in nanoscale cages of zeolites as studied by deuteron spin-lattice relaxation.

Deuteron spin-lattice relaxation was applied to study translational and rotational mobility of CD(4) molecules trapped in the cages of zeolites. Tetrahedral methane molecules are treated as quantum rotators. Relaxation rates related to the intraquadrupole interaction are derived for the T and A+E symmetry species in the presence of large tunneling splittings, consistently with the assumption that A and E species molecules relax at the same rate. An exchange model is presented, which describes the effect on relaxation of CD(4) jumping between two positions characterized by different potentials. While staying at either position bonded to an atom or ion at the cage wall, the molecule has some freedom to move in the vicinity. This causes a time-dependent external electric field gradient, which contributes to the deuteron relaxation rate via the electric quadrupole interaction. Spin conversion transitions couple the relaxation of magnetizations M(T) and M(AE), which is taken into account by reapplying the presented model under somewhat different conditions. Such a two-step procedure leads to successful fits with the experimental results obtained in the range of temperatures roughly 20-200 K for zeolites HY, NaA, and NaMordenite. At higher temperatures CD(4) molecules fly freely across zeolite cages and relaxation changes accordingly, while incoherent tunneling dominates for immobile molecules below 20 K.

Deuteron NMR spectra of ammonium ion isotopomers at low temperatures.

Partially deuterated ammonium compounds contain ammonium ion isotopomers with relative abundances given by the binomial distribution of protons and deuterons. All isotopomers with deuterons contribute characteristic deuteron NMR spectra at 5K. Experimental NMR spectra were separated and respective contributions of isotopomers were determined. The derived contributions agree with expected values for a given deuteration in the case of ammonium hexafluorophosphate. In ammonium hexachlorotellurate both NH2D2+ and about 50% of NH3D+ ions are rigid, while the remaining NH3D+ perform limited jumps. NHD3+ and ND4+ ions undergo tunnelling rotation, NH3D+ ions perform either jumps about C2 axis or limited jumps, but some stay rigid in ammonium hexachlorostannate. NH2D2+, NHD 3+ and ND4+ undergo rotational tunnelling. In the case of ammonium perchlorate, the NH3D+ ions perform either jumps about C3 axis or limited jumps whilst some remain rigid. Very low values of activation energies were derived for all spectral components from the temperature dependence of their spectra, up to about 20K, which indicates an incoherent tunnelling nature of the observed dynamic processes. The diverse mobility of NH3D+ ions appears to be the most interesting and new feature.

Deuteron NMR study of the diverse mobility of the ammonium ions in the ordered phase of (ND4)2PtCl4.

A detailed description of the diverse mobility of the ND4+ ions in the low-temperature ordered phase of (ND4)2PtCl4 is developed on the basis of single-crystal deuteron NMR spectra and site-selective T1 measurements. The ordered phase of (ND4)2PtCl4 consists of two kinds of domains in which the orientation of the ND4+ tetrahedra differs by a 90 degrees rotation about an axis which otherwise is a two-fold symmetry axis of the tetrahedra. Inside the domains, the ND4+ ions do not reorient at low temperatures. The domains are separated by domain walls which contain, according to the deuteron NMR spectra, about 10% of all ND4+ ions. These ions are highly mobile even at 10 K. On rising the temperature, the thickness of the domain walls increases, that is, the ions in more and more layers become mobile. Moreover, we provide evidence for fluctuations of the locations of the domain walls. The central resonance of the domain-wall ions shows a complicated structure below 36 K. On the basis of a tunnelling hypothesis we make an attempt to account for this structure. There are indications that the tunnelling process is incoherent.

Deuteron NMR spectra of ND4ClO4 single crystal at low temperatures.

2H NMR spectra of ND4ClO4 single crystal were obtained at v0 = 44 MHz. Orientation and temperature (1.9-75 K) dependences were measured. Fitting the spectra gives the effective quadrupole coupling constants for all deuterons and the ground torsional level structure. The isotope reduction of the (A-T) and (A-E) tunnelling splittings, i.e., the ratios of the respective splittings for NH4+ and ND4+, were found to be different. The splittings at T = 24 K are about 60% of the helium temperature values. The spectrum undergoes intermediate narrowing by reorientations between 26 and 34 K and tunnelling related features in the spectra are eradicated. After reaching the extreme narrowing limit, a doublet with gradually decreasing separation was observed, what was attributed to averaging by torsional oscillations of increasing amplitude. At high temperatures (T > 75 K), the narrow spectrum reflects fast multiaxial reorientation of the ammonium ion.