Magic peak

Figure 16. Mass distribution of TimCj clusters generated from the reactions of titanium with CH4. Note the "super magic" peak corresponding to TisCu. Taken with permission from ref. 92.

Note, however, that the magic peaks observed do not correspond, as for MgC 2, to perfect met-car clusters. A regular, face-sharing double cage would correspond to the stoichiometry Zri4C2i. The assignment of the most intense peak of that series to Zri3C22 implies the presence of a carbon atom at one metal site (Fig. 7c). ... 

Figure Bl.6.12 Ionization-energy spectrum of carbonyl sulphide obtained by dipole (e, 2e) spectroscopy [18], The incident-electron energy was 3.5 keV, the scattered incident electron was detected in the forward direction and the ejected (ionized) electron detected in coincidence at 54.7° (angular anisotropies cancel at this magic angle ). The energy of the two outgoing electrons was scaimed keeping the net energy loss fixed at 40 eV so that the spectrum is essentially identical to the 40 eV photoabsorption spectrum. Peaks are identified with ionization of valence electrons from the indicated molecular orbitals.

The well-resolved C=0 li peak in the fenchone XPS provides an excellent opportunity to examine PECO from a single, well-characterized initial orbital. As has been previously mentioned, it might be thought that such a localized, spherically symmetric initial orbital would not be sensitive to the molecular enantiomer s handedness, but as can be seen in Fig. 15 (a) the dichroism in the electron yield recorded at the magic angle is sufficiently large to be easily visible by eye as a difference in the intensity of the Icp and rep spectra. 

Figure 15. Circular dichroism of the C=0 C li peak (BE = 292.7 eV) in fenchone at three different photon energies, indicated, (a) Photoelectron spectrum of the carbonyl peak of the (1S,4R) enantiomer, recorded with right (solid line) and left (broken line) circularly polarized radiation at the magic angle, 54.7° to the beam direction, (b) The circular dichroism signal for fenchone for (1R,4A)-fenchone (x) and the (lS,41 )-fenchone (+) plotted as the raw difference / p — /rep of the 54.7° spectra, for example, as in the row above, (c) The asymmetry factor, F, obtained by normalizing the raw difference. In the lower rows, error bars are included, but are often comparable to size of plotting symbol (l/ ,4S)-fenchone (x), (lS,4R)-fenchone (+). Data are taken from Ref. [38],...

We used modifications of the standard solid-state CP-MAS (cross-polarisation, magic-angle spinning) experiment to allow the proton relaxation characteristics to be measured for each peak in the C spectrum. It is known that highly mobile, hydrated polymers can not be seen using either usual CP-MAS C spectrum or solution NMR (6). We found, however, that by a combination of a long-contact experiment and a delayed-contact experiment we could reconstruct a C spectrum of the cell-wall components that are normally too mobile to be visible. With these techniques we were able to determine the mobility of pectins and their approximate spatial location in comparison to cellulose. 

Obviously this is a little difficult to interpret, although with experience you can train yourself to extract all the frequencies by eye... (only kidding ) The FID is a time domain display but what we really need is a frequency domain display (with peaks rather than cosines). To bring about this magic, we make use of the work of Jean Baptiste Fourier (1768-1830) who was able to relate time-domain to frequency-domain data. These days, there are superfast algorithms to do this and it all happens in the background. It is worth knowing a little about this relationship as we will see later when we discuss some of the tricks that can be used to extract more information from the spectrum. 

Figure 1 Schematic representation of the 13C (or 15N) spin-lattice relaxation times (7"i), spin-spin relaxation (T2), and H spin-lattice relaxation time in the rotating frame (Tlp) for the liquid-like and solid-like domains, as a function of the correlation times of local motions. 13C (or 15N) NMR signals from the solid-like domains undergoing incoherent fluctuation motions with the correlation times of 10 4-10 5 s (indicated by the grey colour) could be lost due to failure of attempted peak-narrowing due to interference of frequency with proton decoupling or magic angle spinning.

Variations in star formation history should be imprinted on the s- and r-process ratios as well, however their interpretation can be more complicated because of uncertainties in their exact sources (and thus yields). Y and Ba trace the first and second peak in neutron magic number, respectively, and can be used to examine r-process yields in very metal-poor stars. However, they also have a significant contribution from the s-process in AGB stars, which dominates their production with increasing metallicity. Since AGB s-process yields are thought... 

Neutron capture processes give rise to the so-called magic-number peaks in the abundance curve, corresponding to closed shells with 50, 82 or 126 neutrons (see Chapter 2). In the case of the s-process, the closed shells lead to low neutron-capture cross-sections and hence to abundance peaks in the neighbourhood of Sr, Ba and Pb (see Fig. 1.4), since such nuclei will predominate after exposure to a chain of neutron captures. In the r-process, radioactive progenitors with closed shells are more stable and hence more abundant than their neighbours and their subsequent decay leads to the peaks around Ge, Xe and Pt on the low-A side of the corresponding s-process peak. 

In the same way as for Ceo and C70 fullerenes, boron clusters with magic numbers B5+ and Bi3+ appear as prominent peaks in mass spectra. These boron clusters were calculated for various geometries by several authors and were considered to present 3D aromatic stabilization.297-299... 

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