Anregung von Kristallgitterschwingungen durch Elektronenstrahlen

The interaction of electrons with lattice vibrations in thin films of LiF, NaF, MgO, and Al₂O₃ has been studied by means of high resolution electron energy spectroscopy. Just above the excitation energy of the transversal optical modes small bands in the energy loss spectrum are observed. According to the dielectric theory of an unbounded medium only longitudinal optical modes should be excited. The observed energy loss spectrum may be explained by the excitation of surface lattice vibrations. A theoretical energy loss spectrum of LiF has been computed taking into account the surface effects. It is in excellent agreement with the experimental spectrum. Apart from electrons with energy loss also electrons with energy gain were observed. The intensity distribution of the energy gain spectrum is equivalent to the energy loss spectrum. Energy loss and gain spectra of fast electrons by excitation of lattice vibration are corresponding to the Stokes- and Antistokes lines of spectroscopy of light optics.     

Phononenspektroskopie von Ammoniumchlorid und Ammoniumbromid mit keV-Elektronen

The high resolution energy loss spectrum of NH₄Cl in the spectral region of internal lattice vibration has been reinvestigated. In order to assure the assignement made, the spectra of the deuterated ammonium halides ND₄Cl and ND₄Br has been studied too. The structure of the films, which were investigated, was checked by electron-diffraction and by electron microscopy. The deuterated films show the shift of energy losses towards lower energy losses as expected. Unshifted losses are assigned to partially deuterated material. Two types of spectra are observed for NH₄Cl depending on the size of the crystals and presumably on the perfectnes of the lattice. Unlike the external vibrations, which are strongly influenced by surface effects, at least for the strongest bands good agreement is found with the absorption measurement concerning the positions of the peaks.     

Ammonium dynamics in the disorder a-phase of K1- x (NH4) x Y (Y=Cl,Br, I). a neutron scattering study

Temperature and concentration effects on the lattice parameters and the amplitude weighted phonon density of states (AWPDS) in the mixed salts of ammonium-potassium halides were investigated by neutron powder diffraction (NPD) and incoherent inelastic scattering (IINS). In the disorder α-phase (NaCl type), ammonium ions perform a fast stochastic reorientation at phonon frequencies rate, down to ca. 80 K. The IINS spectra at 10 K displayed the four distinct ammonium excitations, two (resonant) modes below and two (localised) above the cut-off frequency of the AWPDS of potassium halides. The high frequency localised modes correspond to the translational and librational vibrations of NH₄ ions. These modes are typical for ordered phases of ammonium halides. Ammonium concentration effects on the localised and resonant modes were studied for the K_{1? x} (NH₄) _x I mixed salts and the harmonic excitations of ammonium in the hypothetical low temperature α-phase of NH₄I were approximated to ca. 30, 95, 155 and 250 cm^?1. In the real low temperature ordered γ-phase of NH₄I, translational ammonium vibrations were observed at ca. 140-160 cm^?1 and librational at ca. 300 cm^?1.     

Electron energy loss spectra and X-ray photoelectron spectra of Ca2V2O7

We have measured the electron energy loss spectra of Ca₂V₂O₇ in the reflexion mode, at incident energies between 200 and 2400 eV, and the X-ray photoelectron spectra excited by Al K α radiation. The abundant loss structures observed can be correlated with the possible interband transitions, collective oscillations, and excitation of O2s and V3p electrons within the V₂O₇^4- ion. The gap width and molecular orbital (MO) spread (or splitting) is about l eV larger in the V₂O₇^4- ion than in its component VO₄^3- ion. Excitation of O2s states, which may occur together with some MO over-gap transitions, displaces the collective oscillations about 7 eV towards lower energies. Deeper V3p electrons are excited with a maximum energy loss some 7 eV above their binding energy. Cross transitions from Ca3p levels into some empty states of the V₂O₇^4- ion, or direct transitions to available states of the Ca²⁺ ion could not be unambiguously identified. The energy dependence of the excitation cross section and of the electron penetration depth results in a significant variation of the relative intensity of various losses over the investigated energy range.     

Energieverluste monochromatisierter 30 keV-Lithiumionen an Argon und Äthylen

The energy loss spectra of 30-keV Li₇ ⁺ ions after interaction with argon and ethylene have been studied. Wien filters were used as monochromator and energy analyzer, an energy resolution of 0.2 eV was achieved. The ion energy loss spectra obtained differ from those taken with electrons at the same primary energy mainly in two points: In the ion spectra energy losses are found with strong intensities corresponding to optically forbidden transitions which are not excited by fast electrons. Furthermore in the energy range beyond the first ionization limit energy losses appear which are due to charge transfer into excited states of the lithium atom and re-ionization.     

Wirkungsquerschnitte für die Anregung von Molekülschwingungen durch schnelle Elektronen

The differential cross section for the excitation of infra-red inactive and — in dipole approximation — infra-red active fundamental vibrations by fast electrons is calculated. The energy loss spectra of CO₂, N₂O, C₂H₄ are measured with 33 keV electrons in the small energy loss range up to 0.5 eV. The experimentally determined “particular” cross sections

$$\sigma = \int\limits_{\vartheta = 0}^{1.1 \cdot 10^{ - 4} } {d\sigma }$$     

Electron energy loss study of titanium dioxide,barium titanate and silica in the range between 0.02 and 2eV

This work discusses the energy loss spectra of TiO₂, BaTiO₃, silica, and graphite in the range between 0.02 and 2eV. The observed energy losses of crystalline TiO₂ and BaTiO₃ are located energetically between the excitation energies of the transversal and longitudinal optical phonons. This means that the energy losses are due to three (TiO₂) or two (BaTiO₃) different types of surface phonons. The energy loss spectra of the amorphous TiO₂, BaTiO₃, and silica are broadened and show certain similarities to the one-phonon density of states like Raman and infra-red absorption spectra. Rather sharp energy losses in the spectrum of the amorphous TiO₂ are partially interpreted as vibrational excitation of TiO or TiO₂ molecular states.In the energy loss range between 0.2 and 2eV the spectra of the amorphous and crystalline polar material are due to the coupling of the beam electrons to the electromagnetic field of the transition radiation. In the spectrum of graphite, however, which is referred to as comparison, the excitation of the almost free conduction electrons predominates.Part of this work has been presented at the Third International Conference on Thin Films Basic Problems, Applications and Trends, Budapest, Hungary, 1975 [1] and at the International Conference on Lattice Dynamics, Paris 1977 [2]     

Low energy electron spectroscopy of N2 in the 11.8–13.8 eV energy range

In the 11.8–13.8 eV energy range differential threshold and energy loss spectra of electrons scattered by N₂ molecules have been obtained at an incident energy of 14.3 eV and with a 30 meV experimental resolution. The study of the angular behaviour of the observed peaks permits us to distinguish between singlet-singlet and singlet-triplet transitions. The predicted F³Π_u and G³Π_u Rydberg states are observed. Also some levels of unknown triplet states are seen at 13.155, 13.395 and 13.635 eV.     

Untersuchung der Anregung innerer Elektronen von Alkalihalogenidmolekülen im Energieverlustspektrum von 25 keV-Elektronen

The energy loss spectra of 25-keV electrons after interaction with alkali halide vapors were measured. For the energy losses in the energy rangeE?6eV the positions of the peaks are consistent with light absorption measurements considering the energy resolution of the loss spectra. At higher energy peaks were observed, which correspond to the excitation of inner electrons belonging to the alkali atoms. From electron diffraction diagramms it follows, that for the lithium halides the concentration of dimers is considerable.     

Interaction of Electrons with Indole,Tryptophan, and their Derivatives in the Gas Phase

The electron energy loss spectra (EELS) of indole, 3-indolyl propionic acid, 3-indolealdehyde, 3-dimethylaminomethylindole, tryptophan, and N-acetyl-L-tryptophan in the gas phase upon excitation by monokinetic electrons with an energy of E₀ = 11–50 eV are obtained. The structure of EELS is determined in the main by the indole chromophore; the side groups, except for the C=O group of 3-indolealdehyde, exert an insignificant influence. The energy of the lower triplet level ³L_a is 3.3 eV for indole and its derivatives and 3.2 eV for tryptophan and N-acetyl-L-tryptophan. Four singlet transitions in the region of 4.4–7.2 eV have been identified. The molecules studied, except for tryptophan, fluoresce in the gas phase on excitation by electrons. At low values of E₀ (10–25 eV), the fluorescence spectra are similar and are due to the indole fluorophore. Just as in the case of optical excitation, fluorescence on excitation by electrons is associated with the ¹L_b-S₀ transitions. An increase in the energy E₀ up to 60–80 eV leads to dissociation of a portion of the indole molecules and to the appearance of additional bands in the fluorescence spectrum. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 468–472, July–August, 2005.     

Fermi resonance and vibrational analysis of SiH2 ( ) based on the LIF excitation spectra of the transitions

SiH₂ radicals were generated in a free jet by the 193 nm photolysis of phenylsilane and the LIF excitation spectra of vibrationally excited SiH₂ ( ) were observed. The spectra were utilized to determine the vibrational frequencies and anharmonic constants for the symmetric stretching and the bending vibrations. Analysis of the Fermi resonance between the (100) and (020) levels gave interaction energy of 12.4 cm⁻¹.     

The low-energy thermal excitation spectrum of nitrogen molecules adsorbed on Ni(110): Implications for molecular adsorption sites

The adsorption of N₂ molecules on Ni(110) has been investigated by high-resolution He-atom energy-loss spectroscopy. Two external vibrations in the subthermal (< 30 meV) energy regime at 5.75 and 4.5 meV have been observed and are shown to imply the existence of two different adsorption sites, which are assigned to an on-top and a bridge-site. This finding is at variance with the interpretation of data from electron energy loss spectroscopy and InfraRed (IR) spectroscopy, where only one mode of the internal stretch vibration v₁ at frequencies is observed for the chemisorbed nitrogen molecules. A reanalysis of previously published high-resolution IR data reveals that the presence of the second unexpected adsorbate species correlates with a feature in the IR spectra, which previously has been assigned to N₂ molecules adsorbed at defect sites. These findings reveal that in this case the external vibrations are significantly more sensitive to different adsorption sites than the internal vibration, the latter exhibiting a difference between on-top and bridge sites of less than 6 cm^–1.     

Optical investigations of the metal-insulator transition in a low-dimensional organic conductor (EDT-TTF)4[Hg3I8]

The polarized reflectance spectra of single crystals of the low-dimensional organic conductor (EDT-TTF)₄[Hg₃I₈] undergoing a metal-insulator phase transition at a temperature T < 35 K have been presented. The spectral region of the study is 700–6000 cm^?1 (0.087–0.74 eV), and the temperature range is 300–9 K. It has been shown that the reflectance spectra are determined by a system of quasi-free electrons of the upper half-occupied molecular π-orbitals, which form a half-filled metallic band in the crystals. A high anisotropy of the spectra and their temperature dependences have been found. For two polarizations, the quantitative analysis of the spectra at 100 and 25 K has been performed in the framework of the phenomenological Drude model, the effective mass and the width of the initial metallic π-electron band have been deter-mined, and it has been found that the conducting system in the crystals has a quasi-one-dimensional character. As temperature decreases, the spectra demonstrate substantial changes indicating the formation of the energy gap (or pseudogap) in the spectrum of electronic states in the range of ～1500–2500 cm^?1. In the low-frequency region (700–1600 cm^?1), a vibrational structure has been observed, and the most intense feature of the structure (ω = 1340 cm^?1) is caused by the interaction of electrons with intramolecular vibrations of the C=C bonds of the EDT-TTF molecule. For temperatures of 15 and 9 K, the analysis of the spectra has been performed in the framework of the theoretical “phase phonon” model taking into account the interaction of electrons with the intramolecular vibrations. It has been concluded that the metal-insulator transition observed in the reflectance spectra of the crystals is similar to the Peierls dielectric transition that occurs in a system of electrons coupled with the intramolecular vibrations of the molecules forming the crystal.     

Optical properties of BiTeI semiconductor with a strong Rashba spin-orbit interaction

We have modeled the 4f ¹-5d ¹ absorption spectrum of a LiYF₄:Ce³⁺ crystal at zero temperature using a microscopic model of the electron-phonon interaction and the real spectrum of LiYF₄ lattice vibrations. Effects caused by mixing of the wave functions of different states of the 5d ¹ excited configuration of the Ce³⁺ ion, which is induced by the electron-phonon interaction, are considered based on the calculations of the second-, third-, and fourth-order exact moments of curvature of the spectrum envelope. We have shown that the large value of the splitting between the maxima of the bands in the absorption spectrum that correspond to transitions to the third and fourth 5d ¹ levels is a result of the nonadiabatic interaction of 5d electrons with lattice vibrations.     

填充式方钴矿化合物CeOs4Sb12近藤相互作用的非弹性中子散射研究

CeOs₄Sb₁₂晶体中由于导电电子与Ce³⁺ 4f¹电子之间存在c-f杂化作用导致费米面附近存在能量间隙.这种c-f近藤相互作用和能量间隙是理解CeOs₄Sb₁₂物理性质，如近藤绝缘体行为、Ce³⁺磁矩在低温下猝灭以及重费米性等电、磁性质的关键.当用LAM-D中子谱仪对粉末CeOs₄Sb₁₂进行测量时，可以得到不同温度下CeOs₄Sb₁₂的非弹性中子散射谱.结果表明CeOs₄Sb₁₂中存在近藤相互作用，其作用强度为3.1 meV，证实了CeOs₄Sb₁₂为近藤绝缘体.中子测量得出CeOs₄Sb₁₂德拜温度为317 K. 关键词： 非弹性中子散射 填充式方钴矿 近藤绝缘体     

Low temperature heat capacity and magnetic excitation of HoAl2 in a magnetic field

The specific heat of single crystalline HoAl₂ in magnetic fields up to 7.5 T has been measured for the temperature range 1.5–16 K. In addition the energy of a magnetic excitation in a magnetic field of 5 T at 4.2 K has been determined by inelastic neutron scattering. The results have been interpreted with a cubic crystalline electric field and an exchange interaction using the same parameter set B₄=-0.85×10^-4 meV, B₆=+0.71× 10^-6 meV and T_C=31.5 K previously obtained by magnetization measurements.     

Electron-hole liquid in GaS

Photoluminescence spectra of “pure” GaS are recorded under high excitation levels and low temperatures between 1.9 and 10K. This work reports a new and broad band which dominates the spectrum at high excitation intensities and temperatures near 1.9K. Its dependence on the excitation level is highly superlinear. When temperature is raised from 1.9 to 10K the spectrum observed of low excitation levels is recovered. We interpret the band here observed as due to radiative recombination from electron-hole droplets. From best fitting between experimental spectrum and calculated theoretical curves the critical density and the condensation energy are estimated as, n_c = 4.5 × 10²⁰ cm^?3 and φ = 9.0 meV.     

Electron-phonon interaction in non-polar quantum dots induced by the amorphous polar environment

We propose a Fröhlich-type electron-phonon interaction mechanism for carriers confined in a non-polar quantum dot surrounded by an amorphous polar environment. Carrier transitions under this mechanism are due to their interaction with the oscillating electric field induced by the local vibrations in the surrounding amorphous medium. We estimate the corresponding energy relaxation rate for electrons in Si nanocrystals embedded in a SiO₂ matrix as an example. When the nanocrystal diameter is larger than 4 nm then the gaps between the electron energy levels of size quantization are narrow enough to allow for transitions accompanied by emission of a single local phonon having the energy about 140 meV. In such Si/SiO₂ nanocrystals the relaxation time is in nanosecond range.     

Vibrational spectra of (NH4)3ZnCl5

IR and Raman spectra of (NH₄)₃ZnCl₅ have been recorded. The observed spectra have been analysed on the basis of the vibrations of ZnCl ₄ ²⁻ and NH ₄ ⁺ ions. The appearance of multiple Raman bands indicates the presence of two different types of ammonium ions. The effect of anisotropic crystalline field over the ZnCl₄ and NH₄ tetrahedra is also discussed. The assignment of internal modes has been verified by the potential energy distribution calculations.     

Formation of electronically excited states in ultrathin Alq3 films during electron bombardment

Electronic and vibrational electron energy loss spectra are studied on ultrathin Alq₃ films for different electron energies, thicknesses, and temperatures of the film. The shape of the spectrum and the position of the lines are very weakly dependent on the film thickness, indicating weak interaction between the adsorbed molecules and the platinum substrate. The temperature dependence of the vibrational bands is weak. The positions of the triplet and singlet maxima are close to gas-phase and thin-film data obtained for high electron energy. Interference of electrons is observed in measuring the energy loss spectra. The effect of dipole and collisional excitation mechanisms is shown. From the similarity between the energy loss spectra it follows that the nature of the interaction between low-energy electrons and organic materials is the same in gas and thin-film phases, and likewise for the characteristics of the motion of the electrons. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 786–791, November–December, 2006.