Raman spectra of different carbonaceous materials of astrophysical interest

We present here the Raman spectra of 9 different carbonaceous materials of astronomical relevance, including single polycyclic aromatic hydrocarbons and mixtures. Eight of 9 samples show two main bands falling respectively at around 1600 and 1350 cm⁻¹ which imply that all the materials are composed by randomly oriented structural units varying from 50 to 80 Å in size. Further bands and/or shoulders appear in some cases between 800 and 1700 cm⁻¹ (6 and 12 μm) and are attributed to CC or CH_n (n = 1,2,3) functional groups. The coronene spectrum is the only one which does not present any significant band although it shows a very high level of fluorescence. These results provide information about candidate materials which may account for unidentified IR bands observed in astronomical sources.     

Excited states dynamics under high pressure in lanthanide-doped solids

Emission related to rare earth ions in solids takes place usually due to 4fⁿ→4fⁿ and 4fⁿ⁻¹5d¹→4fⁿ internal transitions. In the case of band to band excitation the effective energy transfer from the host to optically active impurity is required. Among other processes one of the possibilities is capturing of the electron at the excited state and the hole at the ground state of impurity.The latest results on high pressure investigations of luminescence related to Pr³⁺ and Eu²⁺ in different lattices are briefly reviewed. The influence of pressure on anomalous luminescence and 4fⁿ⁻¹5d¹→4fⁿ luminescence in BaSrF₂:Eu²⁺ and LiBaF₃:Eu²⁺ systems and Pr³⁺ 4fⁿ→4fⁿ emission quenching is presented and discussed. A theoretical model describing the impurity-trapped exciton as a system where a hole is localized at the impurity and an electron is captured by Coulomb potential at Rydberg-like states is developed. The results show the importance of local lattice relaxation for the creation of stable impurity-trapped exciton states. The ligands shifts create a potential barrier that controls the effect of mixing between the Rydberg-like electron and localized electron wave functions.     

Isotopieverschiebungskonstanten von Th,U, Pu und Am

The isotope shifts of unperturbed electron configurations have been determined from isotope shift measurements in the spectra of Th, U, Pu, and Am. The screening of the 7s electron charge density at the nucleus by 6d, 7s, and 7p electrons is discussed. It turns out that the same screening factors as for the 6s electron in lighter elements can be used. The screening of the 7s electron charge density at the nucleus by one 5f electron amounts to about 25%: [δT(f ⁿ s)?δT(f ⁿ )]/[δT(f ⁿ }s)?δ(f ^n} )]=0.7₅. The charge density at the nucleus due to the filleds (andp _1/2) shells is considerabely screened by anf electron. The isotope shiftδT(f^n}-1 d ^m +2)?δT(f ⁿ d ^m ) produced by this effect is of the same order of magnitude as the isotope shiftδT(f ⁿ d ^m s)-δT(f ⁿ d ^m ) due to ans electron. The experimental isotope shift constants are found to be:Β C _exp(Th²³⁰–Th²³²)=880±120;Β C _exp(U²³³–U²³⁵)=1000±180;Β C _exp(U²³⁴–U²³⁶)=1070±200;Β C _exp(U²³⁶–U²³⁸)=1080±180;Β C _exp(Pu²³⁸–Pu²⁴⁰)=1200±120;Β C _exp(Pu²³⁹–Pu²⁴¹)=1060±100;Β C _exp(Pu²⁴⁰–Pu242)=900 ±90;Β C _exp(Am²⁴¹–Am²⁴³)=890±50 [10^?3cm^?1]. The ratiosΒ C _exp/C _th are discussed.     

Measurements of transition probabilities for doubly ionized vanadium

Transition probabilities of 43 doubly ionized V lines have been measured in the spectral range 2280–3600 Å. These lines belong to the 3d²4s–3d²4p transition array. Emission spectroscopy was used to obtain line intensities. The spectra were emitted from a He plasma with added VOCl₃ vapour in a wall-stabilized arc.     

Revised model for 5d electrons in the heavy rare earth metals

A revised version of a recently published model for 5d electrons in the ferromagnetic state of the heavy rare earth metals is described. The model involves the broadening of local 5d states into overlapping bands with individual widthsW. In the new approach it is assumed that the local 5d wave functions lie at some point between those for atomic 4f _n 5d 6s ² configurations and those calculated for such configurations subject to the restriction that the 4f shell is kept with its moment rigidly fixed in some given direction. The admixture of non-aligned 4f states as in the atom lowers the local energy, but it also lowers the 5d bandwidth due to misfit of the 4f states which occur with and without the presence of a 5d electron. This second effect raises the energy of the low lying states in the band. The best local states are determined by minimising the total electronic energy of the system, using approximations which are most suitable for 4f shells with large excitation energies. Bandwidths are found by fitting the observed saturation magnetic moments in Gd and Tm, and satisfyW?1 eV.     

Electron density diagnostics by Fe XXII line intensity ratio

The electron density of a tokamak plasma is obtained from the 114.41 and 117.17Å line intensities of Fe XXII. This measurement is found to be useful for electron densities in the range 10¹²−10¹⁵ cm⁻³, on account of its weak dependence on temperature and of the proximity of these spectral lines.     

Influence of one CO molecule on structural and electronic properties of monatomic Cu chain

By using first-principles calculations, we have systematically investigated the structural and electronic properties of an infinite linear monatomic Cu chain with an adsorbed CO molecule. We find that the bridge geometry is energeticabsally favored not only when the Cu–Cu bond below the molecule is unstretched, but also for a wide range of d_Cu–Cu up to about 4.20 Å, while the substitutional geometry is favored only in the hyperstretched situation d_Cu–Cu>4.80 Å. Charge density differences point out the electron transfer is from the Cu atoms to the adsorbed CO molecule. The binding mechanism of CO to Cu chain can be described by the Blyholder’s model, in terms of σ-donation of electron density from the nonbonding CO-5σ orbital into empty metal orbitals and π-backdonation from the occupied metal d orbitals to empty CO-2π^⁎ orbital. The donation/backdonation process leads to the formation of bonding/antibonding pairs, 5σ_b/5σ_a and 2π_b^⁎/2π_a^⁎, with the 5σ_a lying above E_f and the 2π_b^⁎ below E_f.     

High-lying odd configurations of quintuply ionized bismuth (Bi VI)

The spectrum of Bi VI in a wavelength region of 177–431 Å was studied. The transitions from the levels of the interacting configurations 5d ⁸6s6p+5d ⁹7p+5d ⁹5f+5d ⁹6f to the levels of the 5d ¹⁰ and 5d ⁹6s configurations were analyzed. 174 spectral lines were identified, and 79 new levels of high-lying odd configurations of Bi VI were found.     

Zero point shift in rare earth doped CaF2

The line position of the 4f ⁷(⁸ S _7/2)→4f ⁶5d (4130 Å) transition in Eu:CaF₂ has been measured as well as its shift under the action of uniaxial stress. These data are used to estimate the isotope shift due to the zero point vibrations. There is reasonable agreement with that measured directly in Sm:CaF₂.     

UV absorption of RbAg4I5-RE (Sm, Yb) thin-film systems

UV spectra of samples prepared by vacuum deposition of Sm and Yb thin films on 100–200-nm thick films of the RbAg₄I₅ solid electrolyte (SE) at 300–350 K contain strong absorption bands peaking at about 4.3 and 5.0 eV. After deposition of ～5 nm of Sm, the ionic conductivity σ of the samples decreases from σ ₀ to ≈0.9 σ ₀, and the SE lattice parameter, from 11.24 to ≈11.15 Å, with the x-ray reflection halfwidth increasing from 0.5 to 0.8°. Further growth of Sm concentration in the samples changes the x-ray diffraction pattern, the absorption at 4.3 and 5.0 eV increases, a new absorption edge forms at 3.8 eV, and σ decreases down to ～10^?2 σ ₀. It is conjectured that the strong UV absorption bands in heavily defected silver halides of the RbAg₄I₅-Sm(Yb) system is genetically related to the 4d ¹⁰→4d ⁹5s electronic transitions in free Ag⁺ ions.     

The quantum space-time of c = −2 gravity

We study the fractal structure of space-time of two-dimensional quantum gravity coupled to c = −2 conformal matter by means of computer simulations. We find that the intrinsic Hausdorff dimension d_H = 3.58 ± 0.04. This result supports the conjecture d_H = −2α₁/α₋₁, where α_n is the gravitational dressing exponent of a spinless primary field of conformal weight (n + 1, n + 1), and it disfavours the alternative prediction d_H = 2/|γ|. On the other hand, 〈lⁿ〉 ∼ r²ⁿ for n > 1 with good accuracy, i.e. the boundary length l has an anomalous dimension relative to the area of the surface.     

Band analysis of the Swan system (d3Πg-a3Πu) of 13C2 and 12C13C molecules

The emission spectrum of the d³Π_g-a³Π_u system (Swan bands) due to ¹³C₂ and ¹²C¹³C molecules has been obtained in a low pressure hollow cathode discharge through a mixture of argon and benzene containing enriched ¹³C (90%). The spectrum was photographed on a 3.4-m Ebert spectrograph (reciprocal dispersion 0.54 Å mm^?1 in the first order). Isotope effect measurements have been carried out to determine the shift between isotopic bands and those emitted by ordinary molecules. The rotational analysis of six ¹³C₂ bands and three bands of ¹²C¹³C has been performed and molecular constants were derived.     

Resonant inelastic x‐ray scattering from highly correlated dysprosium compounds

Dy₂O₃ and Dy metal's resonant inelastic x‐ray scattering (RIXS) spectra were measured in the Beijing Synchrotron Radiation Facility. As a bulk sensitive probe and two‐photon process, RIXS provides more information on the electronic structure of matter. In this full RIXS experiment, the 2p⁶4fⁿ→ 2p⁵4fⁿ5d¹ (2p⁵4f^{n + 1}5d⁰) → 2p⁶3d⁹4fⁿ5d¹ (2p⁶3d⁹4f^{n + 1}5d⁰) channel of two samples (Dy₂O₃ and Dy metal) was studied. Further comparison shows that there are many differences in the RIXS spectra. Dy metal has only a single resonance and its 5d band is broader than that of Dy₂O₃. In the resonant regime, it has a lower final state energy, whereas in the non‐resonant regime it exceeds Dy₂O₃. This causes a broader bandwidth of the main final state B and a narrower bandwidth in the resonant and non‐resonant regime. The pre‐edge structure in Dy L₃ absorption spectra was also resolved using RIXS, which cannot be seen in conventional XAS owing to 2p core hole lifetime broadening. Copyright © 2005 John Wiley & Sons, Ltd.     

Autoionizing and highly excited states in the spectrum of triply ionized tin Sn IV

Transitions from autoionizing states in the spectrum of Sn IV in the range 200–630 Å, occurring due to the excitation of electrons from the inner 4d ¹⁰ shell, are investigated with high resolution. The transitions from the 4d ⁹5p ², 4d ⁹5s6p, and 4d ⁹5snf (up to n = 9) configurations are identified and their autoionization widths are measured. Transitions from the highly excited 4d ¹⁰ ns (n = 8–10), 4d ¹⁰6p, and 4d ¹⁰7d configurations are also revealed and the ionization potential of Sn IV is refined. The data obtained are compared with the results of calculations by the Hartree-Fock and semiempirical methods.     

Raman spectroscopic study of the selenite mineral mandarinoite Fe2Se3O9·6H2O

Selenites and tellurites may be subdivided according to formula and structure. There are five groups, based upon the formulae (a) A(XO₃), (b) A(XO₃·) xH₂O, (c) A₂(XO₃)₃·xH₂O, (d) A₂(X₂O₅) and (e) A(X₃O₈). Of the selenites, molybdomenite is an example of type (a); chalcomenite, clinochalcomenite, cobaltomenite and ahlfeldite are minerals of type (b); mandarinoite Fe₂Se₃O₉·6H₂O is an example of type (c). Raman spectroscopy has been used to characterise the mineral mandarinoite. The intense, sharp band at 814 cm⁻¹ is assigned to the symmetric stretching (Se₃O₉)⁶⁻ units. Three Raman bands observed at 695, 723 and 744 cm⁻¹ are attributed to the ν₃ (Se₃O₉)⁶⁻ anti‐symmetric stretching modes. Raman bands at 355, 398 and 474 cm⁻¹ are assigned to the ν₄ and ν₂ bending modes. Raman bands are observed at 2796, 2926, 3046, 3189 and 3507 cm⁻¹ and are assigned to OH stretching vibrations. The observation of multiple OH stretching vibrations suggests the non‐equivalence of water in the mandarinoite structure. The use of the Libowitzky empirical function provides hydrogen bond distances of 2.633(9) Å (2926 cm⁻¹), 2.660(0) Å (3046 cm⁻¹), 2.700(0) Å (3189 cm⁻¹) and 2.905(3) Å (3507 cm⁻¹). The sharp, intense band at 3507 cm⁻¹ may be due to hydroxyl units. It is probable that some of the selenite units have been replaced by hydroxyl units. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the mixed anion mineral yecoraite Bi5Fe3O9(Te4+O3)(Te6+O4)2·9H2O

Tellurates are rare minerals as the tellurate anion is readily reduced to the tellurite ion. Often minerals with both tellurate and tellurite anions are found. An example of such a mineral containing tellurate and tellurite is yecoraite. Raman spectroscopy has been used to study this mineral, the exact structure of which is unknown. Two Raman bands at 796 and 808 cm⁻¹ are assigned to the ν₁(TeO₄)²⁻ symmetric and ν₃(TeO₃)²⁻ antisymmetric stretching modes and Raman bands at 699 cm⁻¹ are attributed to the ν₃(TeO₄)²⁻ antisymmetric stretching mode and the band at 690 cm⁻¹ to the ν₁(TeO₃)²⁻ symmetric stretching mode. The intense band at 465 cm⁻¹ with a shoulder at 470 cm⁻¹ is assigned the (TeO₄)²⁻ and (TeO₃)²⁻ bending modes. Prominent Raman bands are observed at 2878, 2936, 3180 and 3400 cm⁻¹. The band at 3936 cm⁻¹ appears quite distinct and the observation of multiple bands indicates the water molecules in the yecoraite structure are not equivalent. The values for the OH stretching vibrations listed provide hydrogen bond distances of 2.625 Å (2878 cm⁻¹), 2.636 Å (2936 cm⁻¹), 2.697 Å (3180 cm⁻¹) and 2.798 Å (3400 cm⁻¹). This range of hydrogen bonding contributes to the stability of the mineral. A comparison of the Raman spectra of yecoraite with that of tellurate containing minerals kuranakhite, tlapallite and xocomecatlite is made. Copyright © 2009 John Wiley & Sons, Ltd.     

Particle-hole multiplets in 40Ca observed in the 41Ca(τ, α) reaction

Energy levels in ⁴⁰Ca up to 10.2 MeV have been studied in the neutron pickup reaction ⁴¹Ca(τ, α)⁴⁰Ca with 20 MeV bombarding energy. Thirty excited states have been identified and angular distributions have been measured in the interval from 5° to 40° by means of a split-pole magnetic spectrometer. The angular distributions together with DW calculations have been used to extract l_n values and spectroscopic factors. The l_n = 2 strength distribution for the $\text{f}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}\text{d}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}{}^{\mathrm{?1}}$ particle-hole levels is compared to the l_p = 3 strength distribution from pr stripping data.     

Total dielectronic recombination rate coefficient for Co-like tungsten

Ab initio calculation of the total dielectronic recombination (DR) rate coefficient from the ground state 3s²3p⁶3d⁹(J=5/2) of Co-like tungsten is performed employing the relativistic distorted-wave approximation with configuration-interaction. The DR contributions mainly come from complex series 3d⁸4ln′l′. The complex series 3p⁵3d¹⁰n′l′, 3p⁵3d⁹4ln′l′ and 3d⁸5ln′l′ also contribute significantly to the total DR rates at relatively high electron temperatures. The l′ and n′ dependences of the partial rate coefficient are investigated. The inclusion of decays into autoionizing levels followed by radiative cascades (DAC) enlarges the total DR rate coefficients by a factor of about 10%. The level-by-level extrapolation method is developed to include DAC effects. The total DR rate coefficients are fitted to an empirical formula. It is shown that at temperatures above 2.5 keV the Burgess-Merts (BM) semiempirical formula can provide DR results with an accuracy of about 15%, whereas at electron temperatures below 100 eV it underestimates the DR rate coefficients by up to a few orders of magnitude and its temperature dependence is completely inadequate. The comparison of the results for Ni-like and Co-like tungsten shows that these two sets of DR rate coefficients are very close in magnitude at relatively high electron temperatures.     

Jet emission spectra in the Schumann region: The L2Σ− → A2Πi transition of CN

The emission spectrum of the CN radical in the ultraviolet and Schumann regions from approximately 3500 to 1500 Å has been photographed in higher orders of a 10.6-m concave grating vacuum spectrograph. Of the two sources used to generate the spectra one is a radiofrequency discharge in flowing pure HCN, the other a dc discharge in supersonically expanding Ar seeded with HCN. An extensive system of red-degraded double-headed bands appears in the jet emission spectrum between 2000 and 1500 Å. The bands have a rotational temperature of ∼40 K and arise in transitions from eight vibrational levels of a new ²Σ⁻ electronic state, labeled L²Σ⁻, to the well-known A²Π_i upper state of the CN red system. Vibrational and rotational constants have been determined; the new state has ω_e = 1165.80 and B_e = 1.3337 cm⁻¹. Possible reasons for the lack of emission from v = 2 of L²Σ⁻ are discussed.     

Observation of resonance recombination lines in electron excited auger spectra of Gd

Combined measurements of electron excited N_4,5 Auger spectra and photoelectron emission on clean and oxidized Gd lead to a distinction between Auger lines originating from 4d → continuum and 4d → 4? resonance excitations. Several Auger structures are identified as due to the direct recombination of 4d⁹4?⁸ states with the 4f and valence electrons. The shape of the most prominent Auger line for oxidized Gd agrees perfectly with the Fano profile of the 4? photoemission intensity.