Raman scattering in ZrB<Subscript>12</Subscript> cage glass

High-precision measurements of the Hall effect and Raman scattering have been performed for single crystals of ZrB₁₂ superconductor in the wide temperature range of 5–300 K. For ZrB₁₂, the boson peak with ω_max ~ 100 cm^–1 has been observed for the first time within the low-frequency range of the Raman spectrum I(ω). The sizes of vibrational clusters with the correlation length ranging from 25 to 35 Å are estimated. The relation between the renormalization of the low-frequency density of vibrational states accompanying the transition to the cage-glass phase (T* ~ 90 K) and the enhancement of superconductivity in ZrB₁₂ is discussed.     

Vibrational Analysis of the A3Π0−X1Σ+ and B3Π1−X1Σ+ Subsystems of the GaBr Molecule

Abstract

The emission band spectrum of gallium monobromide has been excited in a dc hollow cathode discharge. bands of the ³Π_0,1?X¹Σ⁺ system, lying in the range from 340 to 370 nm have been recorded at high resolution and measured. The previous vibrational analysis has been revised and corrected. New vibrational assignment has been proposed and improved vibrational constants of the upper and lower electronic states have been determined.     

Effect of amorphization on the electronic and lattice specific heat of an Ni2B alloy

The specific heats of the Ni₂B amorphous system and of its crystal analog were studied in the temperature range 3–270 K. The data obtained permitted us to isolate the contribution due to atomic vibrations from the experimentally measured specific heat, determine the electronic density of states at the Fermi level and the temperature dependence of the characteristic Debye parameter Θ, and to calculate some average frequencies (moments) of the vibrational spectrum. The electronic density of states at the Fermi level increases under amorphization. An analysis of the temperature dependence of the lattice specific heat showed that amorphization brings about a substantial growth in the density of vibrational states at low frequencies, whereas the spectrum-averaged and rms frequencies change very little, which is in good agreement with neutron diffraction measurements.     

Vibrational and electronic properties of the amorphous systems Ni<Subscript>44</Subscript>Nb<Subscript>56</Subscript>, Ni<Subscript>62</Subscript>Nb<Subscript>38</Subscript>, and Cu<Subscript>33</Subscript>Zr<Subscript>67</Subscript> as derived from specific heat measurements

The specific heats of the amorphous systems Ni₄₄Nb₅₆, Ni₆₂Nb₃₈, and Cu₃₃Zr₆₇ were studied in the temperature range 3–273 K. The data obtained allow one to isolate the contribution due to atomic vibrations from the experimentally measured specific heat, to determine the density of electronic states at the Fermi level and the temperature dependence of the characteristic Debye parameter Θ over a broad temperature range, and to calculate a few frequency moments that characterize the vibrational spectrum. The information derived on the average characteristics of vibrational spectra is in good agreement with earlier data on inelastic neutron scattering. In transferring from Ni₄₄Nb₅₆ to Ni₆₂Nb₃₈, the density of electronic states at the Fermi level decreases and the characteristic vibrational frequencies increase. The density of electronic states at the Fermi level for Cu₃₃Zr₆₇ is close to that for Ni₆₂Nb₃₈. The characteristic frequencies of the vibrational spectrum of the Cu₃₃Zr₆₇ system are substantially lower (by 30%) than those of the Ni₄₄Nb₅₆ and Ni₆₂Nb₃₈ systems.     

New measurements of the microwave spectrum of formamide

New measurements of the microwave spectrum of formamide have been obtained in the frequency range from 49 to 340 GHz using the microwave spectrometer at the Institute of Radio Astronomy of NASU, Kharkov, Ukraine. An analysis of the rotational spectra of the ground, v₁₂, v₉, v₁₁ and 2v₁₂ excited vibrational states of the main isotopic species as well as of the ground states of the ¹³C, ¹⁵N and ¹⁸O substituted species has been carried out using SPFIT/SPCAT programs. The analysis of a strong Coriolis interaction coupling between v₉, v₁₁ and 2v₁₂ vibrational states of formamide has been also fulfilled as well as the analysis of the quadrupole hyperfine structure of the observed transitions. For the first time the quadrupole coupling parameters for the excited vibrational states and for the ¹⁸O substituted species of formamide were determined.     

The Rotational Spectrum of Fluoroethyne (HCCF) Revisited

The pure rotational spectrum of fluoroethyne (fluoroacetylene, HCCF) has been reinvestigated. Rotational transitions have been measured in the frequency range from 230 up to 510 GHz and assigned to the excited vibrational states (υ₃υ₄υ₅)=(000), (001), (002), (003), (010), (011), (012), (020), and (100). The analysis of the spectrum extends the spectroscopic data for HCCF by correcting and refining the rotational and rovibrational constants determined in our previous investigation.     

Density of vibrational states in amorphous solid media: Measurement by single-molecule spectroscopy

The energy spectrum of low-frequency vibrational modes in amorphous polyisobutylene doped with chromophore tetra-tert-butylterrylene molecules has been measured. The technique for measuring the spectra of vibrational modes in solid amorphous media by single-molecule spectroscopy is described. The measured spectrum is compared with the data on the density of vibrational states (bosonic peak) in pure polyisobutylene, which were obtained by inelastic neutron scattering. It is shown that incorporation of small amounts of tetra-tert-butylterrylene into polyisobutylene did not significantly change the low-temperature vibrational dynamics of the matrix.     

Submillimeter wave spectrum and molecular constants of N2O

The submillimeter wave spectrum of the N₂O molecule has been investigated within the 375–565 GHz frequency range with a sensitivity better than 10^?8 cm^?1. The measured frequencies include 161 lines with intensities γ ? 10^?6 cm^?1 belonging to 22 spectroscopically different species of the molecule (specifically, the ground and some excited vibrational states of the five most abundant isotopic species of the molecule in natural abundance) with a statisticall and systematic error of the order of magnitude 10^?8. Rotational and two centrifugal stretching constants could be determined for each spectroscopic species. For each isotopic species observed, we have made a general analysis of the spectrum in different vibrational states bearing in mind resonance effects. The total number of the rotational and rovibrational constants obtained exceeds 40.     

Vibrational and electronic characteristics of Zr<Subscript>70</Subscript>Pd<Subscript>30</Subscript>, Zr<Subscript>80</Subscript>Pt<Subscript>20</Subscript> icosahedral quasicrystals and their amorphous Counterparts

The heat capacity of Zr₇₀Pd₃₀ and Zr₈₀Pt₂₀ icosahedral quasicrystals and their amorphous counterparts is studied in the temperature range 1.5–500 K in order to establish a correlation between the short-range atomic order and the physical properties of these compounds. A comparison of the data made it possible to reveal changes in the vibrational spectra within the low-and high-energy ranges, as well as in the density of states, superconducting characteristics, electron-phonon interaction, and anharmonicity of the lattice thermal vibrations and to calculate the main average frequencies (moments) characterizing the vibrational spectra. The lower superconducting transition temperature T _c of the quasicrystals as compared to that of the amorphous counterparts can be associated with the decrease in the density of states on the Fermi surface, the hardening of the phonon spectrum, and the weakening of the electron-phonon coupling.     

On the nature of a lattice vibrational mode at a frequency of 135 cm−1 in Hg1 − x Cd x Te alloys

The vibrational spectrum of a cadmium impurity atom in the HgTe crystal has been calculated using the microscopic theory of lattice dynamics in the approximation of a low impurity concentration. Within this theory, the behavior of the local and quasi-local modes induced upon substitution of the lighter Cd atom for the Hg atom in the region of the zero or very low one-phonon density of states in the HgTe crystal has been considered. It has been found that, apart from the local mode at a frequency of 155 cm^?1, the calculated vibrational spectra exhibit a weak (but clearly pronounced) feature at a frequency of 134 cm^?1, which coincides with the experimentally observed vibrational mode (the “minicluster” mode) at a frequency of 135 cm^?1 in the Hg_{1 ? x} Cd _x Te (x = 0.2–0.3) alloys at 80 K.     

Microwave spectrum of deuterated silyl isocyanate,SiD3NCO

The microwave spectrum of SiD₃NCO has been observed and analyzed for 18 different vibrational states in the ν₁₀ manifold. Some accidental resonances have been observed and analyzed. The vibrational dependence of the rotational and l-doubling constant and centrifugal distortion constant D_JK has been successfully interpreted in terms of the two-dimensional anharmonic oscillator model.     

Rotational spectrum of ONCl in the (0, 0, 1) and (0, 1, 0) vibrational states and “b” type spectrum in the ground state. Comparison of force field obtained by different combinations of experimental data

From the rotational spectrum of ONCl in (0, 0, 1) and (0, 1, 0) excited vibrational states the inertia defects in these states have been determined. The “b” type rotational spectrum in the ground state has also been measured allowing the determination of Δ⁰ and of all the first-order centrifugal distortion constants.It is shown that by using differences of inertia defects Δ₂ and Δ₃ together with centrifugal distortion constants which do not involve the planarity relations and with harmonic vibrational frequencies of two isotopic species, the harmonic vibrational frequencies of two other isotopic species can be satisfactorily predicted.By using only inertia defects differences Δ₂ and Δ₃ as extra data, a definite choice can be made among the three sets of force constants which equally well reproduce the harmonic frequencies of four isotopic species.     

Submillimeter-wave spectroscopy of HCN in excited vibrational states

Measurements of the rotational spectrum of HCN in excited vibrational states have been extended to higher-J values. The transitions reach J=8←7 around 710 GHz for most vibrational states studied in this investigation and J=22←21 near 2 THz for the (020) and (030) vibrational states. Using a pure sample of gaseous HCN at 350 K, selected states up to one quantum in the C–H stretching vibration at 3311.5 cm⁻¹ have been investigated. Even transitions having two quanta in the C–H stretch could be studied employing a glow discharge in a gas mixture of CH₄ and N₂. Molecular constants in 13 vibrational states have been obtained, several of which have been studied for the first time by rotational spectroscopy. The vibrational temperature in the discharge system is found to be about 1500 K for the stretching vibrational modes and about 600 K for the bending states.     

Microwave spectrum ofcis 3-fluorophenol

The microwave spectrum ofcis 3-fluorophenol involving rotational states up toJ=28 has been observed and analysed in the frequency range 23–25 GHz in the ground vibrational state at room temperature. Analysis yields three rotational and five quartic centrifugal distortion constants. A tentativer ₀ structure has been proposed satisfying the observed rotational constants. The small value of the inertia defect Δ=0·07 confirms the planarity of the conformer.     

Rotation-vibration analysis of the microwave spectrum of cyanobutadiyne,H(CC)2CN

The detailed rotational spectrum of the linear molecule cyanobutadiyne, H(CC)₂CN, has been observed in the range 26.5 to 40.0 GHz. In particular, a study has been made of transitions belonging to the vibrationally excited states (including combination states) of the degenerate vibrations ν₁₀ and ν₁₁. Particular attention has been focused upon two series of satellites: one in which v₁₁ = 1–8 and a second in which v₁₀ = 1 while v₁₁ varies from 1–7 for a given J transition. The analysis was performed using a least-squares criterion to fit all the transitions simultaneously. In addition to providing confirmation of the forms of the vibrational and rotational l-resonance matrix elements, the analysis has demonstrated that the widely spaced l quartets observed in combination states with odd Σ_iv_i can be attributed to a strong mixing of the four l = 1 states by vibrational l resonance. It has also been found that it is only possible to determine the sign of the product of the offdiagonal parameters and not the sign of any one parameter. Therefore the reported assignment is not unique. As confirmation of the validity of the analysis, the computer simulation of the spectrum is compared with that observed.     

The infrared spectrum of 12C2HD: the stretching–bending combination bands in the 1800–4700 cm−1 region

The infrared spectrum of ¹²C₂HD has been observed between 1800 and 4700?cm^?1 by Fourier transform spectroscopy. The ν₁, ν₂ and ν₃ absorption bands and the associated hot and combination bands involving the bending modes up to υ_t?=?υ₄?+?υ₅?=?2 have been investigated. Altogether, 60 vibrational bands were analysed, leading to the spectroscopic characterization of 31 vibrationally excited states. Several perturbations have been observed, but the transitions involving the perturbing states have not been detected. As a consequence, an appropriate treatment of the vibrational or ro-vibrational interactions has not been possible. A tentative assignment of the perturbing states has been proposed. Eventually, global fits for each fundamental vibration and its associated cold and hot bands have been performed.     

Specific heat of small vanadium particles in the normal and superconducting state

The specific heat C of ultrafine vanadium particles of various diameters (2.9–13 nm) has been measured in the temperature interval 1.5–12 K and in magnetic fields up to 3.5 T. Both the vibrational and electronic contributions to C in the normal state are strongly enhanced as compared to the bulk behavior. For not too small particles (> ～10nm), the vibrational specific heat can be interpreted in terms of the discrete phonon spectrum of free elastically vibrating small spheres while, at low temperatures, the vibrational specific heat of the smallest particles is predominantly due to Einstein modes which are attributed to low-frequency vibrations of weakly bound surface atoms. Level quantization does not appear to play a detectable role in the electronic specific heat of the normal state. Rather, the observed enhancement must be attributed to an increased electronic density of states at (100) surfaces of bcc metals or to electronic states of substoichiometric V-oxides. The transition range to superconductivity progressively broadens with decreasing particle size due to fluctuations. In this temperature range, the electronic specific heat behaves in qualitative agreement with theoretical predictions.     

High-resolution overtone spectra of molecular complexes

A high-resolution spectrum of the acetylene–water complex has been recorded in the overtone range. Two bands of C₂H₂–D₂O were analysed, corresponding to the overtone excitations of either the acetylene or the water units. The vibrational shifts and the upper states rotational constants were retrieved, demonstrating that the geometry of the complex is only slightly modified by the excitation. A larger linewidth was observed for the 2CH band than for the 2OD?+?DOD band, probably due to the direct coupling of the 2CH excitation with the dissociation coordinate.     

Vibrational dynamics of Fe in amorphous Fe–Sc and Fe–Al alloy thin films

The atomic vibrational dynamics of ⁵⁷Fe in 800-Å thick amorphous (a-) ⁵⁷Fe_0.25Sc_0.75, a-⁵⁷Fe_0.67Sc_0.33 and a-⁵⁷Fe_0.14Al_0.86 alloy thin films has been investigated at room temperature by nuclear resonant inelastic X-ray scattering (NRIXS) of synchrotron radiation. The amorphous phase has been successfully stabilized by codeposition of Fe and Sc or Al in ultrahigh vacuum onto substrates held at –140 °C during deposition. The amorphous structure of the samples was confirmed by X-ray diffraction and conversion electron Mössbauer spectroscopy. The ⁵⁷Fe-projected partial vibrational density of states, g(E), has been obtained from the measured NRIXS vibrational excitation probability, together with thermodynamic quantities such as the probability of recoilless absorption (f-factor), the average kinetic energy per Fe atom, the average force constant, and the vibrational entropy per Fe atom. A plot of the reduced density of states, g(E)/E², versus excitation energy E proves the existence of non-Debye-like vibrational modes (boson peak) with a peak energy, E _bp , in the range of 3–7 meV. Both, the boson peak height H _bp and E _bp were found to depend on the composition. Above the boson peak, g(E)/E² exhibits an exponential decrease. Our results demonstrates that the features of the boson peak depend on the amount and type of element M (M = Al, Si, Mg, Sc).     

Neutron scattering studies of solid-state polymorphism in dimethyl butanol glass formers

Inelastic incoherent neutron scattering (IINS) and neutron powder diffraction (NPD) studies have been performed for two dimethyl 1-butanols and two dimethyl 2-butanols with CH₃ side molecular groups. Low-temperature vibrational density of states confirmed solid-state polymorphism detected by calorimetric methods, i.e., existence of crystalline and ODIC phases for all isomers, orientationally disordered glass for 2,2-DM 1-B and 3,3-DM 2-B, and glass of isotropic phase for 3,3-DM 1-B. Difference in vibrational density of states between glass and the ordered crystal has shown the so-called Boson peak. Influence of the OH group position in the molecules on their vibrational dynamics up to 50 meV is discussed.