Broadband excitation pulses for high‐field solid‐state nuclear magnetic resonance spectroscopy

In nuclear magnetic resonance spectroscopy, experimental limits due to the radiofrequency transmitter and/or coil means that conventional radiofrequency pulses (“hard pulses”) are sometimes not sufficiently powerful to excite magnetization uniformly over a desired range of frequencies. Effects due to nonuniform excitation are most frequently encountered at high magnetic fields for nuclei with a large range of chemical shifts. Using optimal control theory, we have designed broadband excitation pulses that are suitable for solid‐state samples under magic‐angle‐spinning conditions. These pulses are easy to implement, robust to spinning frequency variations, and radiofrequency inhomogeneities, and only four times as long as a corresponding hard pulse. The utility of these pulses for uniformly exciting ¹³C nuclei is demonstrated on a 900 MHz (21.1 T) spectrometer. Copyright © 2012 John Wiley & Sons, Ltd.     

Anion effects on the phase transition of N‐isopropylacrylamide hydrogels

NMR spectra were collected for poly(N‐isopropylacrylamide) (PNIPAAm) hydrogel using high‐resolution magic angle spinning (HRMAS) after gel pieces were hydrated in the presence of D₂O, NaF, NaCl, and NaI aqueous solutions. Changes in the peak height intensity of the spectra provide quantitative insight into the phase transition process. The thermodynamic values of the phase transition were calculated using a van't Hoff analysis of the NMR data. Unlike the trend observed for decreases in the (LCST), changes in the enthalpy and entropy did not clearly display a linear dependence with respect to salt concentration. Rather, it was observed that increases in salt concentration did not affect the enthalpy and entropy to the extent as the initial change observed between no salt and 100 mM solutions. Finally, the effect of salts on the hysteresis of the rehydrating process was observed. Hysteresis occurs due to the need for hydrophobic interactions to break down before water is able to infiltrate the polymer matrix. NaF stabilizes hydrophobic interactions while NaI destabilize hydrophobic interactions, causing them to break down at higher temperatures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Brownian motion on a manifold

The question of the existence and correct form of equations describing Brownian motion on a manifold cannot be answered by mathematics alone, but requires a study of the underlying physics. As in classical mechanics, manifolds enter through the transformation of variables needed to account for the presence of constraints. The constraints are either due to a physical agency that forces the motion to remain on a manifold, or they represent conserved quantities of the equation of motion themselves. Also the Brownian motion is described either by a Smoluchowski diffusion equation or by a Kramers equation. The four cases lead to the following conclusions, (i) Smoluchowski diffusion with a conserved quantity reduces to a diffusion equation on the manifold; (ii) The same is true for diffusion with a physical constraint in three dimensions, but in more dimensions it may happen thatno autonomous equation on the manifold results; (iii) A Kramers equation with a conserved quantity reduces to an equation on the manifold, but in general not of the form of a Kramers equation; (iv) The Kramers equation with a physical constraint reduces to an autonomous Kramers equation on the manifold only for a special shape of that constraint. Throughout, only a certain type of physical constraints has been envisaged, and global questions are ignored. Finally, the customary heuristic construction of a Fokker-Planck equation for a mechanical system on a manifold is demonstrated for the case of Brownian rotation of a rigid body, and its shortcomings are emphasized.     

Mössbauer spectroscopy of supported bimetallic catalysts: 1∶5 FeM/SiO2 (M=Ru,Rh, Pd,Ir, Pt)

Mössbauer spectra of SiO₂-supported bimetallic FeM (M=Ru, Rh, Pd, Ir, and Pt) with FeM=15 arter treatments such as reduction, exposure to CO and passivation in air are described and compared with previous results obtained on 11 FeM/SiO₂ catalysts.     

Thermal conductivity and specific heat of amorphous Zr0.67Ni0.33 after structural relaxation

Low-temperature measurements of the thermal conductivity (0.3KT5K) and of the specific heatC (0.07KT3.5K) of splat-cooled amorphous superconducting Zr_0.67Ni_0.33(T _c 2.7K) after different annealing stages are reported. increases progressively (up to 55%) after annealing. An analysis of with the help of normal-state measurements belowT _c in an overcritical field shows that the phonon-electron scattering remains unaltered after annealing. Hence the increase in must be entirely attributed to structure-induced (intrinsic) scattering, i.e. by two-level tunneling states (TLS) at low temperatures (T1K). The specific heat shows a small decrease aboveT _c (by 8%) which is attributed to a small diminution of the electronic density of states at the Fermi level and to a small increase in the Debye temperature. ForTT _c where TLS dominate, the specific heatC decreases less upon annealing than expected from the increase of in the standard tunneling model. This points to a change in the TLS relaxation time spectrum upon annealing, as observed previously for Zr _x Cu_1–x glasses.     

Experimental results on radiative muon capture in complex nuclei

Experimental results for the radiative muon capture branching ratio in several nuclei and the photon-muon spin asymmetry in⁴⁰Ca are reported. For the measurements a two arm Nalspectrometer was used. Apart from²⁶O and⁴⁰Ca, where we confirm previous results of our group, new data on¹²C,²⁶Fe,¹⁶⁵Ho and²⁰⁹Bi are presented. No available theoretical models explain all the data consistently. The preliminary results for the asymmetry measurements, obtained using a stroboscopic method are in agreement with previous measurements and with theoretical calculations.Presented at the symposium Mesons and Light Nuclei, Bechyn, Czechoslovakia, May 27–June 1, 1985.