Localized cross-polarization in solids

Single quantum heteronuclear cross-polarization in solids is strongly sensitive to resonance offsets. In the presence of main field- or radio-frequency field gradients, the cross-polarization efficiency, therefore, shows a strong spatial dependence, which represents a new principle for localized NMR in solids. Since slices-selective excitation is achieved simultaneously to cross-polarization, the suggested pulse sequences avoid the use of shaped pulses, the application of which is problematic with solid. The dependence of the localization efficiency on experimental and sample parameters is analyzed theoretically for a spin-1/2 system in the presence of a static or a radio-frequency magnetic field gradient. The resulting slice profiles and the calculated dependence of the slice thickness on the parameters of the basic cross-polarization procedures are discussed and confirmed experimentally on the example of¹H-³C spin systems.     

Ergodicity and efficiency of cross-polarization in NMR of static solids

Cross-polarization transfer is employed in virtually every solid-state NMR experiment to enhance magnetization of low-gamma spins. Theory and experiment is used to assess the magnitude of the final quasistationary magnetization amplitude. The many-body density matrix equation is solved for relatively large (up to N=14) spin systems without the spin-temperature assumption for the final spin states. Simulations show that about 13% of the thermodynamic limit is still retained within the proton bath. To test this theoretical prediction, a combination of a reverse cross-polarization experiment and multiple contacts is employed to show that the thermodynamic limit of magnetization cannot be transferred from high- to low-gamma nuclei in a single contact. Multiple contacts, however, fully transfer the maximum magnetization. A simple diffusion on a cone model shows that slow dynamics can affect the build up profile for the transferred magnetization.     

Indirect NMR detection in solids with multiple cross-polarization periods

The use of indirect detection for signal enhancement in solids is much less common than in liquids, but has attracted renewed interest recently. In this work we describe an indirect detection scheme that offers a large signal enhancement for rare spins in solids. The method uses multiple periods of cross polarization, each followed by an evolution period. The latter is increased stepwise in a pseudo 2D experiment, in which the signal of the rare spin is detected as modulation of the abundant spin. As an illustration of this method, the natural abundance deuterium NMR spectrum of a static powder sample of 1,2,4,5-tetramethylbenzene is presented.     

Infrared spectroscopy of solids

For materials like small gap semiconductors or intercalated layered compounds the general form of the complex dielectric function is: ϵ(ω) = ϵ_x + Δϵ_inter + Δϵ_intra + Δϵ_ph, where ϵ_∞is the high frequency dielectric constant due to all interband transitions except the uppermost valence band and the lowest conduction band, Δϵ_inter is the contribution to the dielectric constant due to this two bands in particular, Δϵ_intra is the contribution due to intraband free carrier transitions and Δϵ_ph is the contribution due to lattice vibrations. The contribution from transitions between valence and conduction bands to the imaginary part of the dielectric function Δϵ_inter(ω,T) for a narrow gap material can be readily calculated in the random phase approximation (RPA) formalism. The real part Δϵ_inter is obtained by performing the Kramers-Kronig inversion on the expression Δϵ_inter. Dielectric function of HgTe between 8 and 300 K is discussed. The interband contribution to the complex dielectric function in a layered intercalation compound is also examined. Pure graphite, first and second stage compounds are treated as an example. Reflectivity and magnetoreflectivity spectra simultaneously determining the plasma and the cyclotron frequencies, allow one to measure the free carrier density, hence the Fermi level, and the effective mass of the carriers. The variation of the effective mass as a function of the position of the Fermi level traces the energy bands dispersion relation. An example of such investigations is given for PbSe layered materials like Bi₂Se₃ are also studied by infrared reflectivity spectroscopy. Intercalation of such materials increases the free carrier population which consequently moves the Fermi level up in the conduction band. Analysis of reflectivity spectra allows an accurate determination of the free carrier concentration and gives a useful tool for the investigation of atom insertion in layered materials. Recent experiments on the intercalation of Li in a certain number of layered materials will be presented. In the frame of the classical theory of independent harmonic oscillators, the phonon contribution to the dielectric function is given by the sum of transverse modes for each oscillator with the corresponding damping parameters and oscillator strength. The complex dielectric function can then be written as a set of separate equations for the real and imaginary parts of the wave-number-dependent dielectric function. In the spectral region when phonon and plasmon frequencies may coincide a strong plasmon-phonon coupling will be experienced. In a simple model with one LO and one TO frequency, one expects two singularities at the two maxima of the function 1m −ϵ⁻¹; representing longitudinal modes. The frequencies generally labeled ω₊ and ω_- correspond to longitudinal oscillations with the lattice and electron plasma vibrating, respectively, in phase and 180° out of phase. In small gap materials the situation is more complex. Because of the particular band structure, the contribution Δϵ_inter(ω) must be included. In some cases it also becomes necessary to include additional oscillators with strong polar character corresponding to a particular defect or to additional vibrations. The implications of all these fundamental concepts in the investigation of high Tc materials is discussed and examples given.     

Photoacoustic spectroscopy of solids

The opto- or photo-acoustic effect used in gas analysis has been extended to the study of solids. This technique provides a simple method for obtaining information about optical absorptions and subsequent de-excitations in solids.     

Homonuclear vanadium-51 dipolar couplings in inorganic solids obtained via hahn spin echo decay NMR spectroscopy

Dipolar dephasing of the magnetization following a Hahn spin echo pulse sequence potentially provides a quantitative means for determining the dipolar second moment in solids. In this work, the possibility of employing Hahn spin echo decay spectroscopy to obtain quantitative ⁵¹V–⁵¹V dipolar second moments is explored. Theoretical spin echo response curves are compared to experimental ones for a collection of crystalline vanadium-containing compounds. This work suggests that ⁵¹V dipolar second moments can be obtained by selectively exciting the central m = 1/2 → −1/2 by a Hahn echo sequence for vanadate compounds with line broadening no greater than approximately 220 ppm. For vanadates with greater broadening of the central transition due to chemical shift, second-order quadrupolar, and dipolar interactions, off-resonance effects lead to an oscillatory time dependence of the spin echo. Experimentally determined second moments of the normalized echo decay intensities lie within 10–33% of the calculated values if the second moments are extrapolated to zero evolution time due to the time scale dependence of spin exchange among neighboring vanadium nuclei. Alternatively, the second moments can be obtained to within 10–25% of the calculated values if the broadening of the central transition due to chemical shift and second-order quadrupolar effects can be estimated.     

Submillimeter BWO spectroscopy of solids

The potentialities of submillimeter spectroscopy (3–30 cm^–1) based on backward wave oscillators for studying solids are discussed. The scope of the research on this problem made at the Institute of General Physics of the USSR Academy of Sciences is outlined.     

Hadamard NMR spectroscopy in solids

The duration of 2D and 3D NMR experiments in solids can be reduced by several orders of magnitude by using frequency domain Hadamard encoding with long selective pulses. We demonstrate Hadamard encoded experiments in (13)C enriched solids samples. To avoid multiple quantum interferences, the Hadamard encoding pulses are applied sequentially rather than simultaneously in this study. Among other possible applications, dipolar assisted rotational resonance experiments and measurement of NOESY type build-up rates in proton driven spin diffusion are demonstrated.     

Threshold photoemission spectroscopy in solids

Threshold photoemission spectroscopy (TPES) is used to measure the Fe 2p spectrum of a stainless steel sample. The obtained spectrum is compared with analogous spectra measured by X-ray photoemission and absorption spectroscopies. The results of this comparison suggest that resonant two-electron autoionization processes, rather than direct photoemission from the core level, are the main mechanisms contributing to the signal. Limits and applicability of this experimental approach to investigate bulk electronic properties in solids are discussed.     

Effects of high intensity ultrasound on inorganic solids

Ultrasonic irradiation dramatically affects the reactivity of a variety of inorganic solids. We have found, for example, large increases in the rates of intercalation of a wide range of compounds into various layered inorganic solids (such as ZrS2, V2O5, TaS2 and MoO3. High intensity ultrasound also enhances the heterogeneous catalysis of alkene hydrogenation by Ni powders. Scanning electron microscopy reveals that ultrasound has multiple effects on the morphology and surface characteristics of inorganic solids, creating substantial surface damage, increasing surface areas significantly and causing increased particle aggregation.     

Comparative electroabsorption studies of organic and inorganic solids

Spectral changes induced by moderate electric fields provide detailed insight into the electronic states of organic and inorganic solids. Although the basic effects, Stark effect and Franz–Keldysh effect, are the same in both types of material, the electroabsorption spectra vary strongly in size and spectral lineshape due to competing interactions. The large variance of the effects is demonstrated by representative examples of high mobility semiconductors, quantum wells, π-conjugated polymers, and charge transfer transitions in single crystals, disordered films and a double-quantum well. It is shown that only high-quality samples reveal the quantum mechanics of field-induced effects which are very sensitive to disorder.     

Photoacoustic infrared spectroscopy of some solids

Infrared spectra in the 100–15000 wavenumber region (0.67–100 m) of some ionic (as LiF) and semiconducting (as Ge, Si, GaAs) powders and crystals are reported. The experiment involves the use of a photoacoustic cell as an accessory to a multiple scan averaging Michelson interferometer. The results show the advantages of studying impurities in powders, and surface properties, particularly since the technique is immune to scattering induced errors.Work presented in part (by D.G.M.) at the 22nd Rocky Mountain Conference, Denver, CO, August 10–14, 1980.     

Electron energy-loss spectroscopy applied to solids

Several illustrating examples of recent electron energy-loss investigations of the electronic structure of solids are reviewed. In particular, studies on rare-gas bubbles in metals, on conducting polymers, and onL _2,3 edges of 3d transition metals are reported. Moreover, the electron energy-loss spectrometer, which was used for these investigations, is described briefly.     

Photoelectron spectroscopy of solids using gas-phase spectrometers

By using continuous deposition of metal surfaces or a continuous scrape technique the ultraviolet photoelectron spectra of clean polycrystalline Zn, Cd, Sn and Pb have been obtained using spectrometers originally designed for gas-phase work. Spectra are calibrated with respect to an internal gas-phase standard. A study of the oxidation of lead is presented to illustrate the applicability of these techniques to adsorption studies. A second oxide in addition to the established orthorhombic form of PbO is observed for low O₂ doses.