Chemical abundances of 11 bulge stars from high-resolution, near-IR spectra

Context. It is debated whether the Milky Way bulge has characteristics more similar to those of a classical bulge than those of a pseudobulge. Detailed abundance studies of bulge stars are important when investigating the origin, history, and classification of the bulge. These studies provide constraints on the star-formation history, initial mass function, and differences between stellar populations. Not many similar studies have been completed because of the large distance and high variable visual extinction along the line-of-sight towards the bulge. Therefore, near-IR investigations can provide superior results. Aims. To investigate the origin of the bulge and study its chemical abundances determined from near-IR spectra for bulge giants that have already been investigated with optical spectra. The optical spectra also provide the stellar parameters that are very important to the present study. In particular, the important CNO elements are determined more accurately in the near-IR. Oxygen and other alpha elements are important for investigating the star-formation history. The C and N abundances are important for determining the evolutionary stage of the giants and the origin of C in the bulge. Methods. High-resolution, near-infrared spectra in the H band were recorded using the CRIRES spectrometer mounted on the Very Large Telescope. The CNO abundances are determined from the numerous molecular lines in the wavelength range observed. Abundances of the alpha elements Si, S, and Ti are also determined from the near-IR spectra. Results. The abundance ratios [O/Fe], [Si/Fe], and [S/Fe] are enhanced to metallicities of at least [Fe/H] = -0.3, after which they decline. This suggests that the Milky Way bulge experienced a rapid and early burst of star formation similar to that of a classical bulge. However, a similarity between the bulge trend and the trend of the local thick disk seems to be present. This similarity suggests that the bulge could have had a pseudobulge origin. The C and N abundances suggest that our giants are first-ascent red-giants or clump stars, and that the measured oxygen abundances are those with which the stars were born. Our [C/Fe] trend does not show any increase with [Fe/H], which is expected if W-R stars contributed substantially to the C abundances. No ""cosmic scatter"" can be traced around our observed abundance trends: the measured scatter is expected, given the observational uncertainties.

Experimental and theoretical investigation of the IR spectra and thermochemistry of four isomers of 2-N,N-dimethylaminecyclohexyl 1-N',N'-dimethylcarbamate

A combined experimental and Density functional theory (DFT) B3LYP/6-311+G* study on the IR spectra of four stable isomers of 2-N,N-dimethylaminecyclohexyl 1-N',N'-dimethylcarbamate was performed. Our theoretical calculations reveal that two new isomers of this compound exist and may be more stable than the known isomers. In addition the entropy, heat capacity, and the enthalpy content of the stable isomers are computed by fitting the calculated data to a standard Shomate equation and IR spectra for the two new isomers are presented.

Exploring new molecular species on the (1)[H, Se, F] singlet potential energy surface: Energetics, structures, IR spectra, and heats of formation

Structural, energetic, and vibrational properties of new molecular species, HSeF and HFSe, the associated transition state, and dissociation fragments are investigated using a state-of-the-art theoretical approach, CCSD(T)/CBS. HSeF is a normal covalently bonded molecule 38.98 kcal mol (1) more stable than the complex HF-Se, which shows an unusual structure with a central fluorine atom and a bond angle of 101.8 degrees.A barrier (Delta G(#)) of 49.01 kcal mol (1) separates the two species. Vibrational frequencies are also quite distinct. Heats of formation are evaluated for the diatomic fragments and HSeF. Final Delta(f)H values depend on the experimental accuracy of those of Se(g) and H(2)Se. (c) 2009 Elsevier B.V. All rights reserved.

IR spectra from mapping of diamond sample JH7b

This data set contains 1851 infrared (IR) spectra, forming a single IR map of diamond sample JH7b. This data set is used to show the application of DiaMap, a computer routine written using PERL, to automatically process diamond IR spectra to obtain quantitative impurity data from them. Full abstract will be added after acceptance of publication.

The rearrangements of naphthyinitrenes: UV/Vis and IR spectra of azirines, cyclic ketenimines, and cyclic nitrile ylides

Ar matrix photolysis of 1- and 2-naphthyl azides 3 and 4 at 313 nm initially affords the singlet naphthyl nitrenes, (1)1 and (1)2. Relaxation to the corresponding lower energy, persistent triplet nitrenes (3)1 and (3)2 competes with cyclization to the azirines 15 and 18, which can also be formed photochemically from the triplet nitrenes. On prolonged irradiation, the azirines can be converted to the seven-membered cyclic ketenimines 10 and 13, respectively, as described earlier by Dunkin and Thomson. However, instead of the o-quinoid ketenimines 16 and 19, which are the expected primary ring-opening products of azirines 15 and 18, respectively, we observed their novel bond-shift isomers 17 and 20, which may be formally regarded as cyclic nitrile ylides. The existence of such ylidic heterocumulenes has been predicted previously, but this work provides the first experimental observation of such species. The factors which are responsible for the special stability of the ylidic species 17 and 20 are discussed.

Alpha element abundances and gradients in the Milky Way bulge from FLAMES-GIRAFFE spectra of 650 K giants

Aims. We present the analysis of the [alpha/Fe] abundance ratios for a large number of stars at several locations in the Milky Way bulge with the aim of constraining its formation scenario. Methods. We obtained FLAMES-GIRAFFE spectra (R = 22 500) at the ESO Very Large Telescope for 650 bulge red giant branch (RGB) stars and performed spectral synthesis to measure Mg, Ca, Ti, and Si abundances. This sample is composed of 474 giant stars observed in 3 fields along the minor axis of the Galactic bulge and at latitudes b = -4 degrees, b = -6 degrees, b = -12 degrees. Another 176 stars belong to a field containing the globular cluster NGC 6553, located at b = -3 degrees and 5 degrees away from the other three fields along the major axis. Stellar parameters and metallicities for these stars were presented in Zoccali et al. (2008, A&A, 486, 177). We have also re-derived stellar parameters and abundances for the sample of thick and thin disk red giants analyzed in Alves-Brito et al. (2010, A&A, 513, A35). Therefore using a homogeneous abundance database for the bulge, thick and thin disk, we have performed a differential analysis minimizing systematic errors, to compare the formation scenarios of these Galactic components. Results. Our results confirm, with large number statistics, the chemical similarity between the Galactic bulge and thick disk, which are both enhanced in alpha elements when compared to the thin disk. In the same context, we analyze [alpha/Fe] vs. [Fe/H] trends across different bulge regions. The most metal rich stars, showing low [alpha/Fe] ratios at b = -4 degrees disappear at higher Galactic latitudes in agreement with the observed metallicity gradient in the bulge. Metal-poor stars ([Fe/H] < -0.2) show a remarkable homogeneity at different bulge locations. Conclusions. We have obtained further constrains for the formation scenario of the Galactic bulge. A metal-poor component chemically indistinguishable from the thick disk hints for a fast and early formation for both the bulge and the thick disk. Such a component shows no variation, neither in abundances nor kinematics, among different bulge regions. A metal-rich component showing low [alpha/Fe] similar to those of the thin disk disappears at larger latitudes. This allows us to trace a component formed through fast early mergers (classical bulge) and a disk/bar component formed on a more extended timescale.

Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 · 3H2O

Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 · 3H2O are recorded and analyzed. The observed bands are assigned on the basis of BrO3 − and H2O vibrations. Additional bands obtained in the region of 3 and 1 modes in [Cu(H2O)6](BrO3)2 are due to the lifting of degeneracy of 3 modes, since the BrO3 − ion occupies a site of lower symmetry. The appearance 1 mode of BrO3 − anion at a lower wavenumber (771 cm−1) is attributed to the attachment of hydrogen to the BrO3 − anion. The presence of three inequivalent bromate groups in the [Al(H2O)6](BrO3)3 · 3H2O structure is confirmed. The lifting of degeneracy of 4 mode indicates that the symmetry of BrO3 − anion is lowered in the above crystal from C3v to C1. The appearance of additional bands in the stretching and bonding mode regions of water indicates the presence of hydrogen bonds of different strengths in both the crystals. Temperature dependent Raman spectra of single crystal [Cu(H2O)6](BrO3)2 are recorded in the range 77–523 K for various temperatures. A small structural rearrangement takes place in BrO3 − ion in the crystal at 391 K. Hydrogen bounds in the crystal are rearranging themselves leading to the loss of one water molecule at 485 K. This is preceded by the reorientation of BrO3 − ions causing a phase transition at 447 K. Changes in intensities and wavenumbers of the bands and the narrowing down of the bands at 77 K are attributed to the settling down of protons into ordered positions in the crystal

FT-IR and FT-Raman study of Nasicon type phosphates, ASnFe(PO4)3 [A=Na2, Ca, Cd]

FT-Raman and FT-IR spectra of ASnFe(PO4)3 [A=Na2, Ca, Cd] were recorded and analyzed. The bands were assigned in terms of the vibrational group frequencies of SnO6 octahedral and PO4 tetrahedral. The spectral analysis shows that the symmetry of corner shared octahedral (SnO6) and the tetrahedral (PO4) are lowered from their free ion symmetry state. The presence of Fe3+ ions disrupts the S–N–O–S–N chain in the structure. This causes distortion of SnO6 and PO4 in the structure of all the compounds. Also it is seen that there are two distinct PO4 tetrahedra of different P–O bond lengths. One of these tetrahedra is linearly distorted in all the title compounds. The PO4 frequencies and bond lengths are calculated theoretically and are in agreement with the experimental values. The presence of PO4 polyanion in the structure can reduce the redox energy and hence reduce the metal oxygen covalency strength in the structure

Using paint to investigate fires: an ATR-IR study of the degradation of paint samples upon heating

Fire investigation is a challenging area for the forensic investigator. The aim of this work was to use spectral changes to paint samples to estimate the temperatures to which a paint has been heated. Five paint samples (one clay paint, two car paints, one metallic paint, and one matt emulsion) have been fully characterized by a combination of attenuated total reflectance Fourier transform infrared (ATR-IR), Raman, X-ray fluorescence spectroscopy and powder X-ray diffraction. The thermal decomposition of these paints has been investigated by means of ATR-IR and thermal gravimetric analysis. Clear temperature markers are observed in the ATR-IR spectra namely: loss of m(C = O) band, >300°C; appearance of water bands on cooling, >500°C; alterations to m(Si–O) bands due to dehydration of silicate clays, >700°C; diminution of m(CO3) and d(CO3) modes of CaCO3, >950°C. We suggest the possible use of portable ATR-IR for nondestructive, in situ analysis of paints.

Nuclear and extended spectra of NGC 1068-I. Hints from near-infrared spectroscopy

We report the first simultaneous zJHK spectroscopy on the archetypical Seyfert 2 galaxy NGC 1068 covering the wavelength region 0.9-2.4 mu m. The slit, aligned in the north-south direction and centred in the optical nucleus, maps a region 300 pc in radius at subarcsec resolution, with a spectral resolving power of 360 km s-1. This configuration allows us to study the physical properties of the nuclear gas including that of the north side of the ionization cone, map the strong excess of continuum emission in the K band and attributed to dust and study the variations, both in flux and profile, in the emission lines. Our results show the following. (1) Mid- to low-ionization emission lines are split into two components, whose relative strengths vary with the position along the slit and seem to be correlated with the jet. (2) The coronal lines are single-peaked and are detected only in the central few hundred of pc from the nucleus. (3) The absorption lines indicate the presence of intermediate age stellar population, which might be a significant contributor to the continuum in the near-IR spectra. (4) Through some simple photoionization models we find photoionization as the main mechanism powering the emitting gas. (5) Calculations using stellar features point to a mass concentration inside the 100-200 pc of about 1010 M(circle dot).

Comparative vibrational spectra of pilosine and epiisopilosine crystals

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Design of Gaussian basis sets to the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, tetraoxochromium (IV) ion, and tetraoxochromium (VI) ion

The Generator Coordinate Hartree-Fock (GCHF) method is employed to design 16s, 16s10p, 24s17p13d, 25s17p13d, and 26s17p Gaussian basis sets for the H ((2)S), O ((3)P), O(2-) ((1)S), Cr(3+) ((4)F), Cr(4+) ((3)F), and Cr(6+) ((1)S) atomic species. These basis sets are then contracted to (4s) for H ((2)S), (6s4p) for O ((3)P), and O(2-) ((1)S), (986p3d) for Cr(3+) ((4)F), (10s8p3d) for Cr(4+) ((3)F), and (13s7p) for Cr(6+) (1S) by a standard procedure. For evaluation of the quality of those basis sets in molecular calculations, we have accomplished studies of total and orbital (HOMO and HOMO-1) energies at the HF-Roothaan level for the molecular species of our interest. The results obtained with the contracted basis sets are compared to the values obtained with our extended basis sets and to the standard 6-311G basis set from literature. Finally, the contracted basis sets are enriched with polarization function and then utilized in the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, [Cr(H(2)O)(6)](3+), tetraoxochromium (IV) ion, [CrO(4)](4-), and tetraoxochromium (VI) ion, [CrO(4)](2-). The respective theoretical harmonic frequencies and IR-intensities were computed at the density functional theory (DFT) level. In the DFT calculations we employed the Becke's 1988 functional using the LYP correlation functional. The comparison between the results obtained and the corresponding experimental values indicates a very good description of the IR-spectra of the molecular ions studied, and that the GCHF method is still a legitimate alternative for selection of Gaussian basis sets. (C) 2003 Elsevier B.V. All rights reserved.

Watson–Crick and Sugar-Edge Base Pairing of Cytosine in the Gas Phase: UV and Infrared Spectra of Cytosine·2-Pyridone

While keto-amino cytosine is the dominant species in aqueous solution, spectroscopic studies in molecular beams and in noble gas matrices show that other cytosine tautomers prevail in apolar environments. Each of these offers two or three H-bonding sites (Watson–Crick, wobble, sugar-edge). The mass- and isomer-specific S1 ← S0 vibronic spectra of cytosine·2-pyridone (Cyt·2PY) and 1-methylcytosine·2PY are measured using UV laser resonant two-photon ionization (R2PI), UV/UV depletion, and IR depletion spectroscopy. The UV spectra of the Watson–Crick and sugar-edge isomers of Cyt·2PY are separated using UV/UV spectral hole-burning. Five different isomers of Cyt·2PY are observed in a supersonic beam. We show that the Watson–Crick and sugar-edge dimers of keto-amino cytosine with 2PY are the most abundant in the beam, although keto-amino-cytosine is only the third most abundant tautomer in the gas phase. We identify the different isomers by combining three different diagnostic tools: (1) methylation of the cytosine N1–H group prevents formation of both the sugar-edge and wobble isomers and gives the Watson–Crick isomer exclusively. (2) The calculated ground state binding and dissociation energies, relative gas-phase abundances, excitation and the ionization energies are in agreement with the assignment of the dominant Cyt·2PY isomers to the Watson–Crick and sugar-edge complexes of keto-amino cytosine. (3) The comparison of calculated ground state vibrational frequencies to the experimental IR spectra in the carbonyl stretch and NH/OH/CH stretch ranges strengthen this identification.

Two-dimensional IR correlation spectroscopy: Sequential events in the unfolding process of the λ Cro-V55C repressor protein

A question often posed in protein folding/unfolding studies is whether the process is fully cooperative or whether it contains sequential elements. To address this question, one needs tools capable of resolving different events. It seems that, at least in certain cases, two-dimensional (2D) IR correlation spectroscopy can provide answers to this question. To illustrate this point, we have turned to the Cro-V55C dimer of the λ Cro repressor, a protein known to undergo thermal unfolding in two discrete steps through a stable equilibrium intermediate. The secondary structure of this intermediate is compatible with that of a partially unfolded protein and involves a reorganization of the N terminus, whereas the antiparallel β-ribbon formed by the C-terminal part of each subunit remains largely intact. To establish whether the unfolding process involves sequential events, we have performed a 2D correlation analysis of IR spectra recorded over the temperature range of 20–95°C. The 2D IR correlation analysis indeed provides evidence for a sequential formation of the stable intermediate, which is created in three (closely related) steps. A first step entails the unfolding of the short N-terminal β-strand, followed by the unfolding of the α-helices in a second step, and the third step comprises the reorganization of the remaining β-sheet and of some unordered segments in the protein. The complete unfolding of the stable intermediate at higher temperatures also undergoes sequential events that ultimately end with the breaking of the H bonds between the two β-strands at the dimer interface.

Cytologically normal cells from neoplastic cervical samples display extensive structural abnormalities on IR spectroscopy: Implications for tumor biology

Fourier-transform IR (FT-IR) spectra of pelleted exfoliated cervical cells from patients with cervical cancer or dysplasia differ from those from normal women. To study the origin of these spectral changes, we obtained the FT-IR spectra of individual cervical cells from normal, dysplastic, and malignant cervical samples. Ninety five percent of normal superficial and intermediate cells displayed two distinct spectral patterns designated A and B, and 5% displayed an intermediate pattern, suggesting extensive structural heterogeneity among these cells. Parabasal and endocervical cells showed pattern B spectra. The spectra of malignant, dysplastic, and other abnormal cells also were characterized. Analysis of FT-IR spectra of over 2,000 individual cells from 10 normal females, 7 females with dysplasia, and 5 females with squamous cell carcinoma revealed that the spectra of normal-appearing intermediate and superficial cells of the cervix from women with either dysplasia or cancer differed from those of normal women. Chemometric and classical spectroscopic analysis showed a continuum of changes paralleling the transition from normalcy to malignancy. These findings suggest that (i) the structural changes underlying the spectroscopic changes are involved in or are a product of cervical carcinogenesis and (ii) the neoplastic process may be more extensive than currently recognized with morphological criteria. This approach may be useful for the structural study of neoplasia and also may be of help in the diagnosis or classification of cervical disorders.