SiOC glasses produced from silsesquioxanes by the aerosol-assisted vapor synthesis method.

In this paper, we describe a new method based on aerosol-assisted vapor synthesis for making glass materials by pyrolysis of readily available silsesquioxanes CH3Si(OCH3)3 and CH3Si(OC2H5)3. Combined powder X-ray diffraction (XRD) and spectroscopic studies in the far infrared region (FIR) showed that under applied conditions the method yielded amorphous materials. Subsequent structural studies with the application of the (29)Si and (13)C MAS NMR, Raman, and middle infrared (MIR) techniques led to the conclusion that the pyrolysis of the silsesquioxane precursors resulted in glass materials with a structure of amorphous silica v-SiO2. In the case of certain glasses prepared from CH3Si(OCH3)3, they were also shown to possess in the structure some Si-C bonds (black glasses), whereas those originated from CH3Si(OC2H5)3 were composites that in addition to the silica glass phase contained domains of free/unbound carbon.

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.

Iterative lineshape analysis of quadrupolar echo spectra of a damped CD(3) quantum rotor: preliminary evidence of a novel mechanism of stochastic spin exchange.

It is demonstrated that the wealth of information about damped quantum rotation of CD(3) groups, contained in quadrupolar echo spectra, can be fully explored in a broad temperature range using a method of iterative analysis of the spectral lineshapes. The recently reported lineshape equation which, apart from the quantum tunneling and the dissipative Alexander--Binsch terms, contains an additional dissipative term having no classical analog is shown to be capable of describing even subtle details of the spectra of a crystal of acetylsalicylic acid--CD(3) oriented specifically in the magnetic field. Preliminary evidence of the occurrence of this novel dissipative mechanism in the system studied is reported. The results obtained seem to suggest that there is no "classical limit" in the dissipative behavior of this system.

MAS NMR studies of carbon-13 spin exchange in durene.

One- (1-D) and two-dimensional (2-D) carbon-13 NMR exchange measurements in powder samples of isotopically normal durene under magic angle spinning (MAS) are reported. The experiments include rotor synchronized 2-D exchange (RS2DE), 1-D magnetization transfer (MT) and time reverse ODESSA (tr-ODESSA). The latter two experiments were performed as a function of several external parameters, including proton decoupling field during mixing time, sample spinning rate and partly, of temperature. The effects of these parameters on the spin exchange induced by spin diffusion and by chemical, or physical exchange, is discussed. Spin exchange between all types of carbons in the durene molecules occurs on the time scale of seconds. From the dependence of the spin exchange rate on the external parameters it is concluded that the process is dominated by spin diffusion. On the basis of these results an upper limit of 10(-16) cm2 s(-1) can be set for the self-diffusion constant in crystalline durene.

Anisotropy of the proton T1 and the low-field relaxation in NH4 ClO4 below 20K.

The spin-lattice relaxation of protons in NH4ClO4 at low temperatures has been studied theoretically and experimentally. The NH4 librational tunneling determines the spin-librational wavefunctions, which are derived first. The dominant transition rates related to the magnetic dipolar interaction between the NH4 protons are then obtained. They reproduce well the angular dependence of the proton relaxation time. When all the transition rates are taken into account, both the temperature and frequency dependence of the relaxation rate agree with our experimental data for a powder sample. Reasons for the non-exponential relaxation are discussed. Apart from the angular dependence of the relaxation rate, they include the tunnel frequency distribution, the coupling to the tunnel reservoir and the effect of deuterons in their natural concentration.