The vibrational spectra and structural properties of Me7Eu2UO2(PO4)5 crystals

We investigate the vibrational spectra of crystals of ternary orthophosphates Me₇Eu₂UO₂·(PO₄)₅ (Me–Na, Rb, Cs) obtained by solid-phase synthesis. We show that in these materials the effect of coordination distorts the geometry of the PO ₄ ³⁻ tetrahedron and decreases its symmetry. We conclude that the PO ₄ ³⁻ tetrahedrons in Me₇Eu₂UO₂(PO₄)₅ occupy two nonequivalent positions in the lattice. The character of manifestation and the number of oscillation frequencies observed allow the assumption that they have the C_3v- and C₂-symmetry. This symmetry of two crystallographically nonequivalent groups of PO ₄ ³⁻ ensures a complete set of bands in the IR absorption spectra of the crystals investigated. We show that these crystals exhibit chain structural motifs. Translated from Zhurnal Prikladnoi Spektroskopii, Vol, 64, No. 4, pp. 467–470, July–August, 1997.     

Carbon nanotube bundles and thin layers probed by micro-Raman spectroscopy

Raman spectra of single-wall carbon nanotubes (CNTs) either in the form of micrometer sized bundles or thin layers prepared by dilution and sonication of powders have been compared. We have been able to collect the Raman spectrum of nanotube bundles that are not in touch with the substrate, and therefore not affected by interactions with the substrate surface. This spectrum resulted to be similar to that of the precursor nanotube powders, whereas relevant changes in the Raman spectrum are detected when the diluted powders form very thin layers on either metallic or insulating surfaces, as probed by confocal microraman imaging on well defined areas of the CNTs layers. In the case of thin layers, the intensity of the Raman D band, detected between 1 320 and 1 340 cm^-1 and ascribed to disorder effects, is strongly enhanced. This enhancement occurs independently on the kind of substrate. Received 2 September 2002 Published online 4 February 2003 RID="a" ID="a"e-mail: sangalet@dmf.bs.unicatt.it     

Femtosecond pump-probe experiments on non-stoichiometric sodium-fluoride clusters

In this paper we present two-color pump and probe spectroscopy on Na₂F, the smallest of the non-stoichiometric sodium-fluoride clusters (Na_nF_n-1), in molecular beams by employing femtosecond laser pulses. The molecules were pumped into the first excited state by one photonic transition and consecutively ionized from there by the second photon. We resolved the wavepacket oscillatory motion involving periodical structural rearrangements in the first excited state of Na₂F with a period of 185 fs. The time-resolved experiments show that sodium fluoride clusters provide interesting features which can be manipulated in optimal control experiments.     

Analysis of the Electronic Vibrational Spectra of Bisanthene by Calculating Normal Modes

At 4.2 K, the quasiline fluorescence and fluorescence-excitation spectra (in the region of the S ₁ S ₀- and S ₂ S ₀ transitions) of bisanthene in n-hexane have been obtained. Using the MO/M8ST method, the calculation of the A _g normal modes in the S ₀, S ₁, and S ₂ electronic states was carried out for the bisanthene molecule; the relative intensities of the transitions in the corresponding vibronic spectra were also calculated. The analysis of the results of calculations and experiment made it possible to draw conclusions on the form of the modes for a number of normal vibrations which are active in the bisanthene vibronic spectra.     

The influence of geometry on the vibronic spectra of quantum aggregates

A study is presented of the localisation of excitonic states on extended molecular aggregates composed of identical monomers arising, not from disorder due to statistical energy shifts of the monomers, induced by environmental interactions (Anderson localisation), but rather simply due to changes in the orientation and geometrical arrangement of the transition dipoles. It is shown further that such small changes nevertheless can have a drastic effect on the shape of the vibronic spectrum of the aggregate. The vibronic spectra are calculated using the ‘coherent exciton scattering’ (CES) approximation whose derivation we generalise to be applicable to aggregates of arbitrary size and geometry.     

Calculation of X-ray and Auger transition rates, lifetimes, X-ray wavelengths, and fluorescence yields of variously ionized silicon atoms

X-ray and Auger transition rates, X-ray wavelengths, and fluorescence yields are calculated for variously ionized silicon atoms with configurations 1s2s^m2pⁿ, m=0-2, n=1-6. The calculation has been performed using the Hartree-Fock atomic model. Intermediate coupling and configuration interaction have been taken into account. The energies and widths are found to be strongly affected by configuration mixing. The results from the present calculation have been compared with those available in the literature. The theoretical K_α hypersatellite and satellite spectra fall into several well-separated regions, corresponding to each of the possible number of spectator electrons in the 2s and 2p shells. The dependence of radiative rates and fluorescence yields on the number of spectator electrons is also investigated.     

Analysis of the hot bands in the 2ν9 band region of propyne-d3

The rovibrational spectrum of 2ν₉ band of CD₃CCH is overlapped by two prominent hot bands identified as (2ν₉⁰+ν₁₀^±1)(E)←ν₁₀^±1(E) and 3ν₉^±1(E)←ν₉^±1(E), where ν₁₀ and ν₉ are the degenerate CCC and CCH bending fundamental vibrations, respectively. Assignment of lines to the transitions of these hot bands were carried out with the help of the high-resolution spectra recorded at ∼195 K and at room temperature. Molecular parameters for these hot bands have been obtained from the rotational analysis of the partially resolved K-structure lines. Only Q-head of the third hot band , originating from the lower 2ν₁₀ state could be identified.     

Studies on some alkali-phosphate glasses containing antimony and iron oxides

The effect of heat treatment on the Fe²⁺/Fe³⁺ ratio in some alkali phosphate glasses containing antimony and iron oxides has been investigated. Differential thermal analysis, Mossbauer spectroscopy, magnetic susceptibility and density measurements as well as the molar volume calculations were used in this study. The obtained data indicate that all glasses show approximately unchangeable stability. It is found, from the area under the Mossbauer absorption spectra that ferrous transformed gradually to ferric ions and the transformation rate constant was found to be 48 min⁻¹. The elapsed time was found to be 160 min. This transformation represents a first-order solid state reaction. The molar magnetic susceptibility measurements confirm the above results.     

Inverse problems of aggregation processes

The coagulation frequency is the key ingredient in the population balance (Smoluchowski) equation of coagulation kinetics. An inverse problem is formulated to extract the coagulation frequency from transient size distributions when these distributions are self-similar. Two numerical examples illustrate the procedure. The first demonstrates the inverse problem for the recovery of singular coagulation frequencies, while the second shows the procedure when self-similarity is approximate. Transient droplet coagulation experiments in a turbulent flow field have been performed. The resulting size distributions are observed to be self-similar. The inverse problem is used to determine the drop coagulation frequency. This frequency shows significant deviation from the coagulation frequencies derived from simple models of drop-drop interactions in a turbulent flow field.