Nuclear structure spectroscopies

NOESY Homonuclear NOE (nuclear Overhauser) spectroscopy To elucidate structure of organic molecules To determine the spatial proximity of nuclei... 

A reevaluation of molecular structure of humic substances based on data obtained primarily from nuclear magnetic resonance spectroscopy, X-ray absorption near-edge structure spectroscopy, electrospray ionization-mass spectrometry, and pyrolysis studies was presented by Sutton and Sposito (2005). The authors consider that humic substances are collections of diverse, relatively low molecular mass components forming dynamic associations stabilized by hydrophobic interactions and hydrogen bonds. These associations are capable of organizing into micellar structures in suitable aqueous environments. Humic components display contrasting molecular motional behavior and may be spatially segregated on a scale of nanometers. Within this new structural context, these components comprise any molecules... 

M. Rosina, The calculation of excited states in the particle-hole space using the two-body density matrix of the ground state, in Proceedings the International Corferenee on Nuclear Structure and Spectroscopy, Vol. 1 (H. P. Blok and A. E. L. Dieperink, eds.), North-Holland, Amsterdam, 1974. 

XRF = X-ray fluorescence spectroscopy, XPS = X-ray photoelectron spectroscopy, AES = Auger electron spectroscopy, XANES = X-ray absorption near edge spectroscopy, RAIR = Reflectance-absorbance infrared spectroscopy, EXAFS = X-ray absorption fine-structure spectroscopy, ECR = Electric contact resistance, NMR = Nuclear magnetic resonance spectroscopy, IPS = Imaging photoelectron spectromicroscopy. 

In our discussion the usual Born-Oppenheimer (BO) approximation will be employed. This means that we assume a standard partition of the effective Hamiltonian into an electronic and a nuclear part, as well as the factorization of the solute wavefunction into an electronic and a nuclear component. As will be clear soon, the corresponding electronic problem is the main source of specificities of QM continuum models, due to the nonlinearity of the effective electronic Hamiltonian of the solute. The QM nuclear problem, whose solution gives information on solvent effects on the nuclear structure (geometry) and properties, has less specific aspects, with respect the case of the isolated molecules. In fact, once the proper potential energy surfaces are obtained from the solution of the electronic problem, such a problem can be solved using the standard methods and approximations (mechanical harmonicity, and anharmonicity of various order) used for isolated molecules. The QM nuclear problem is mainly connected with the vibrational properties of the nuclei and the corresponding spectroscopic observables, and it will be considered in more detail in the contributions in the book dedicated to the vibrational spectroscopies (IR/Raman). This contribution will be focused on the QM electronic problem. 

Although they may be part of a catalyst testing [1-3] programme, investigations focused on revealing the reaction mechanism, such as in-situ Fourier transform infrared (FTIR) in transmission or reflection mode, nuclear magnetic resonance (NMR), X-ray diffraction (XRD), X-ray absorption fine-structure spectroscopy (EXAFS), X-ray photoelectron spectroscopy (XPS), electron microscopy (EM), electron spin resonance (ESR), and UV-visible (UV-vis) and the reaction cells used are not included. For the correct interpretation of the results, however, this chapter may also provide a worthwhile guide. 

Another contribution to variations of intrinsic activity is the different number of defects and amount of disorder in the metallic Cu phase. This disorder can manifest itself in the form of lattice strain detectable, for example, by line profile analysis of X-ray diffraction (XRD) peaks [73], 63Cu nuclear magnetic resonance lines [74], or as an increased disorder parameter (Debye-Waller factor) derived from extended X-ray absorption fine structure spectroscopy [75], Strained copper has been shown theoretically [76] and experimentally [77] to have different adsorptive properties compared to unstrained surfaces. Strain (i.e. local variation in the lattice parameter) is known to shift the center of the d-band and alter the interactions of metal surface and absorbate [78]. The origin of strain and defects in Cu/ZnO is probably related to the crystallization of kinetically trapped nonideal Cu in close interfacial contact to the oxide during catalyst activation at mild conditions. A correlation of the concentration of planar defects in the Cu particles with the catalytic activity in methanol synthesis was observed in a series of industrial Cu/Zn0/Al203 catalysts by Kasatkin et al. [57]. Planar defects like stacking faults and twin boundaries can also be observed by HRTEM and are marked with arrows in Figure 5.3.8C [58],... 

Lippmaa et al. (86) have successfully studied solid state Si NMR of several trimethylsilyl silicate samples using proton-enhanced nuclear induction spectroscopy and magic angle spinning. They showed that the high resolution Si NMR of solids can be useful for structural studies of certain soluble and insoluble silicates, because many of these compounds with well defined molecular structures in the solid state tend to undergo very complicated rearrangements and condensation in solution. (93)... 

The most frequently used techniques for the structural elucidation of photodegradation products are IR spectroscopy, mass spectrometry, elemental analysis, and nuclear resonance spectroscopy. Degradation products for use with these methods... 

TPR, Temperature-programmed reaction XPS, X-ray photoelectron spectroscopy IR, infrared spectroscopy H NMR, proton nuclear magnetic resonance spectroscopy UV-vis, ultraviolet-visible spectroscopy ESR, electron spin resonance spectroscopy TPD, temperature-programmed desorption EXAFS, extended X-ray absorption fine structure spectroscopy Raman, Raman spectroscopy C NMR, carbon-13 nuclear magnetic spectroscopy. 

Atomic spectroscopy is a powerful tool to investigate also nuclear properties, and studies comparing theoretical and experimental results can provide a calibration of nuclear structure calculations, needed e.g., for the interpretation of experiments involving parity non-conservation [63], electric dipole... 

Seeds of the Plantago arenaria plant yield an alkaloid, 4 called arenaine (133) whose structure was assigned by Rabaron et al.9S mainly on the basis of nC nuclear magnetic spectroscopy. 

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