@article {449, title = {C-13 Chemical-Shift Tensor Correlation Via Spin-Diffusion in Solid Tropolone Using Switched-Angle Spinning Spectroscopy}, journal = {Journal of Chemical Physics}, volume = {103}, year = {1995}, note = {J Chem PhysTh657Times Cited:7Cited References Count:42}, month = {Dec 8}, pages = {9844-9854}, abstract = {

In switched-angle spinning spectroscopy (SAS) a sample is spun about different angles, beta, relative to the magnetic field, during various periods of the experiment. In the present work, SAS is combined with two-dimensional exchange spectroscopy in order to correlate carbon-13 chemical shift tensors of the carbonyl (1) and hydroxyl (2) carbons of tropolone. Experiments were performed on a sample enriched to 25 at. \% in each of these sites (at different molecules). At this level of enrichment the dominant exchange mechanism between the two sites involves spin diffusion, The experiment consists of a preparation period during which the sample spins at the magic angle and the magnetization of one of the sites is quenched by means of a selective pulse sequence. During the rest of the experiment the sample spins with its axis away from the magic angle except for a short period just before the detection where the axis is switched to the magic angle in order to select the magnetization to be detected. Experiments were performed for all four possible combinations of the initial and final magnetizations, thus providing chemical shift correlations between carbons 1,1\&$\#$39;,2, and 2\&$\#$39; in the two magnetically inequivalent (but symmetry related) molecules in the unit cell. Combining these results with the known crystal structure of tropolone (neglecting a small tilt between the perpendicular to the molecular plane and the crystallographic c-axis) provides information on the orientation and magnitude of the chemical shift tensors of the two types of carbons, The principal values (in ppm) are sigma(xx)(1)=65, sigma(yy)(1)=33, sigma(zz)(1)=-98, sigma(xx)(2)=77, sigma(yy)(2)=17, and sigma(zz)(2)=-94. Assuming sigma(zz) to be perpendicular to the molecular plane, the orientations of the sigma(yy) s\&$\#$39; are 12 degrees off the C-1=0 bond (toward the hydroxyl carbon) for carbon 1 and 10 degrees off the C-3=C-2 bond (away from the carbonyl carbon) for carbon 2. (C) 1995 American Institute of Physics.

}, keywords = {spectra}, isbn = {0021-9606}, doi = {Doi 10.1063/1.469951}, url = {://WOS:A1995TH65700040}, author = {Larsen, R. G. and Lee, Y. K. and He, B. and Yang, J. O. and Luz, Z. and Zimmermann, H. and Pines, A.} } @article {445, title = {Xenon Nmr-Study of a Nematic Liquid-Crystal Confined to Cylindrical Submicron Cavities}, journal = {Journal of Physical Chemistry}, volume = {99}, year = {1995}, note = {J Phys Chem-UsRm901Times Cited:17Cited References Count:37}, month = {Aug 3}, pages = {11989-11993}, abstract = {

NMR studies of xenon gas dissolved in the liquid crystal ZLI 1132 confined to submicron cylindrical cavities are reported. Spectra taken as a function of temperature yield a clear indication of the nematic to isotropic phase transition of the confined liquid crystals. In the nematic phase at 21 degrees C, the resonance line of dissolved Xe-129 exhibits a chemical shift anisotropy of 15 ppm due to a random distribution of director axes in the plane perpendicular to the long axis of the cylinder. The anisotropy and temperature dependence of the confined system are compared to control experiments that use the bulk liquid crystal. The quadrupolar splitting observed in the Xe-131 NMR spectrum of the confined liquid crystalline solution of xenon gas is slightly greater than that found in the bulk. Two-dimensional exchange NMR demonstrates that the xenon atoms probe different average liquid crystal directors within a single cavity on a 20 ms time scale and that interpore exchange occurs on a time scale of 400 ms. The exchange data indicate that changes in the orientation of the director within individual cavities occur on a length scale of about 2 mu m.

}, keywords = {mixtures}, isbn = {0022-3654}, doi = {Doi 10.1021/J100031a029}, url = {://WOS:A1995RM90100029}, author = {Long, H. W. and Luzar, M. and Gaede, H. C. and Larsen, R. G. and Kritzenberger, J. and Pines, A. and Crawford, G. P.} } @article {464, title = {2-Dimensional Xe-129 Exchange Nmr Measurements of Xenon Dynamics in Na-a Zeolite}, journal = {Zeolites and Related Microporous Materials: State of the Art 1994}, volume = {84}, year = {1994}, note = {Stud Surf Sci CatalPart a-CBd02eTimes Cited:3Cited References Count:21Studies in Surface Science and Catalysis}, pages = {519-526}, abstract = {Two-dimensional (2D) exchange NMR is a powerful tool for measuring the dynamics and energetics of adsorbed xenon atoms undergoing slow exchange between the alpha-cages of Na-A zeolite. In this proceedings, we present recently published results, as well as additional discussion and data obtained, using 2D Xe-129 NMR to determine rate coefficients for intercage xenon hopping and to correlate them with adsorption and activation energies. Variable-temperature experiments establish the activation energy for hopping between alpha-cages to be 60+/-10 kJ/mol. The dependence of these kinetic and thermodynamic quantities on xenon occupancy of the alpha-cages reflects the importance of intracage interactions on the behavior of the adsorbed guest molecules.}, keywords = {cavities}, isbn = {0167-2991}, url = {://WOS:A1994BD02E00063}, author = {Janicke, M. and Chmelka, B. F. and Larsen, R. G. and Shore, J. and Schmidt-Rohr, K. and Emsley, L. and Long, H. and Pines, A.} } @article {461, title = {3-Dimensional Variable-Angle Nuclear-Magnetic-Resonance Exchange Spectroscopy without Rotor Axis Hopping}, journal = {Journal of Chemical Physics}, volume = {101}, year = {1994}, note = {J Chem PhysNy002Times Cited:12Cited References Count:48}, month = {Aug 1}, pages = {1852-1864}, abstract = {

Slow, large-amplitude chain motions play an important role in determining the macroscopic mechanical properties of polymers. Although such motions have been studied quantitatively by two-dimensional (2D) nuclear: magnetic resonance (NMR) exchange experiments, overlapping anisotropic patterns hamper spectral analysis, and limit applications. Variable angle correlation spectroscopy (VACSY) has proven useful in resolving such problems for rapidly spinning samples by separating anisotropic spectral patterns according to isotropic chemical shifts. In a previous study [J. Am. Chem. Sec. 115, 4825 (1993)], we described a three-dimensional (3D) NMR experiment that incorporates; the VACSY method and a hop of the rotor axis to correlate the isotropic chemical shifts to 2D anisotropic exchange patterns. The hop of the rotor axis, however, presents experimental difficulties and limits the range of motional rates that may be studied. We present in this paper a new 3D VACSY exchange experiment that obtains the same correlations without the need for the rotor axis hop. A series of 2D exchange spectra are recorded with the sample spinning at different rotation axis angles.\&$\#$39; Then using the scaling of the anisotropic frequency at the different angles, we construct the data onto a 3D matrix so that a Fourier transformation directly yields the desired correlations. The technique is applied to C-13 exchange NMR to study the slow molecular motion of ordered isotactic polypropylene.

}, keywords = {distributions}, isbn = {0021-9606}, doi = {Doi 10.1063/1.467696}, url = {://WOS:A1994NY00200011}, author = {Lee, Y. K. and Emsley, L. and Larsen, R. G. and Schmidt-Rohr, K. and Hong, M. and Frydman, L. and Chingas, G. C. and Pines, A.} } @article {476, title = {Nmr-Study of Xenon Dynamics and Energetics in Na-a Zeolite}, journal = {Chemical Physics Letters}, volume = {214}, year = {1993}, note = {Chem Phys LettMd614Times Cited:56Cited References Count:22}, month = {Oct 29}, pages = {220-226}, abstract = {

For xenon atoms adsorbed in Na-A zeolite, electronic interactions cause shifts in NMR frequencies, resulting in a spectrum with discrete peaks from xenon atoms in cages with different xenon occupancies. Using two-dimensional exchange NMR, it is possible to determine the microscopic rates of intercage motion and to relate them to the adsorption and activation energies of the xenon atoms. The dependence of the adsorption energies on xenon cage occupancy reflects the importance of the intercage interactions and is directly related to the cage occupancy distribution. Variable temperature measurements yield an activation energy of about 60 kJ/mol for the transfer of a xenon from one cage to another.

}, keywords = {xe}, isbn = {0009-2614}, doi = {Doi 10.1016/0009-2614(93)90085-F}, url = {://WOS:A1993MD61400015}, author = {Larsen, R. G. and Shore, J. and Schmidt-Rohr, K. and Emsley, L. and Long, H. and Pines, A. and Janicke, M. and Chmelka, B. F.} }