Oscillator Strengths and Predissociation Rates for Rydberg Transitions in 12C16O, 13C16O, and 13C18O Involving the E 1Pi, B 1Sigma+, and W 1Pi States

One of the processes controlling the interstellar CO abundance and the ratio of its isotopologues is photodissociation. Accurate oscillator strengths and predissociation rates for Rydberg transitions are needed for modeling this process. We present results on absorption from the E ^1Pi-X ^1Sigma^+ (1-0) and B ^1Sigma^+-X ^1Sigma^+ (6-0) bands at 1051 and 1002 \AA, respectively, and the vibrational progression W ^1Pi-X ^1Sigma^+ (v'-0) bands with v' = 0 to 3 at 972, 956, 941, and 925 \AA, respectively. The corresponding spectra were acquired at the high resolution (R ~ 30,000) SU5 beam line at the Super ACO Synchrotron in Orsay, France. Spectra were obtained for the ^12C^16O, ^13C^16O, and ^13C^18O isotopologues. These represent the most complete set of measurements available. Comparison is made with earlier results, both empirical and theoretical. While earlier determinations of oscillator strengths based on absorption from synchrotron radiation tend to be somewhat smaller than ours, the suite of measurements from a variety of techniques agree for the most part considering the mutual uncertainties. For the bands studied here, their relative weakness, or their significant line widths arising from predissociation, minimizes potential problems from large optical depths at line center in absorption measurements. Predissociating line widths could generally be extracted from the spectra thanks to the profile simulations used in the analysis. In many cases, these simulations allowed us to consider e and f parity levels separately and to determine the dependence of the width on rotational quantum number, J. Our results are consistent with earlier determinations, especially the widths inferred from laser experiments

Wavelength-Dependent UV Photodesorption of Pure N2N_2 and O2O_2 Ices

Context: Ultraviolet photodesorption of molecules from icy interstellar grains can explain observations of cold gas in regions where thermal desorption is negligible. This non-thermal desorption mechanism should be especially important where UV fluxes are high. Aims: $N_2$ and $O_2$ are expected to play key roles in astrochemical reaction networks, both in the solid state and in the gas phase. Measurements of the wavelength-dependent photodesorption rates of these two infrared-inactive molecules provide astronomical and physical-chemical insights into the conditions required for their photodesorption. Methods: Tunable radiation from the DESIRS beamline at the SOLEIL synchrotron in the astrophysically relevant 7 to 13.6 eV range is used to irradiate pure $N_2$ and $O_2$ thin ice films. Photodesorption of molecules is monitored through quadrupole mass spectrometry. Absolute rates are calculated by using the well-calibrated CO photodesorption rates. Strategic $N_2$ and $O_2$ isotopolog mixtures are used to investigate the importance of dissociation upon irradiation. Results: $N_2$ photodesorption mainly occurs through excitation of the $b^1\sqcap_u$ state and subsequent desorption of surface molecules. The observed vibronic structure in the $N_2$ photodesorption spectrum, together with the absence of $N_3$ formation, supports that the photodesorption mechanism of $N_2$ is similar to CO, i.e., an indirect DIET (Desorption Induced by Electronic Transition) process without dissociation of the desorbing molecule. In contrast, $O_2$ photodesorption in the 7−13.6 eV range occurs through dissociation and presents no vibrational structure. Conclusions: Photodesorption rates of $N_2$ and $O_2$ integrated over the far-UV field from various star-forming environments are lower than for CO. Rates vary between $10^{-3}$ and $10^{-2}$ photodesorbed molecules per incoming photon.Astronom

Ferromagnetism in the Strong Hybridization Regime of the Periodic Anderson Model

We determine exactly the ground state of the one-dimensional periodic Anderson model (PAM) in the strong hybridization regime. In this regime, the low energy sector of the PAM maps into an effective Hamiltonian that has a ferromagnetic ground state for any electron density between half and three quarters filling. This rigorous result proves the existence of a new magnetic state that was excluded in the previous analysis of the mixed valence systems.Comment: Accepted in Phys. Rev.

X-ray photodesorption of complex organic molecules in protoplanetary disks -- I. Acetonitrile CH3CN

X-rays emitted from pre-main-sequence stars at the center of protoplanetary disks can induce nonthermal desorption from interstellar ices populating the cold regions. This X-ray photodesorption needs to be quantified for complex organic molecules (COMs), including acetonitrile CH3CN, which has been detected in several disks. We experimentally estimate the X-ray photodesorption yields of neutral species from pure CH3CN ices and from interstellar ice analogs for which CH3CN is mixed either in a CO- or H2O-dominated ice. The ices were irradiated at 15 K by soft X-rays (400-600 eV) from synchrotron light (SOLEIL synchrotron). X-ray photodesorption was probed in the gas phase via quadrupole mass spectrometry. X-ray photodesorption yields were derived from the mass signals and were extrapolated to higher X-ray energies for astrochemical models. X-ray photodesorption of the intact CH3CN is detected from pure CH3CN ices and from mixed 13CO:CH3CN ices, with a yield of about 5x10^(-4) molecules/photon at 560 eV. When mixed in H2O-dominated ices, X-ray photodesorption of the intact CH3CN at 560 eV is below its detection limit, which is 10^(-4) molecules/photon. Yields associated with the desorption of HCN, CH4 , and CH3 are also provided. The derived astrophysical yields significantly depend on the local conditions expected in protoplanetary disks. They vary from 10^(-4) to 10(-6) molecules/photon for the X-ray photodesorption of intact CH3CN from CO-dominated ices. Only upper limits varying from 5x10^(-5) to 5x10^(-7) molecules/photon could be derived for the X-ray photodesorption of intact CH3CN from H2O-dominated ices. X-ray photodesorption of intact CH3CN from interstellar ices might in part explain the abundances of CH3CN observed in protoplanetary disks. The desorption efficiency is expected to vary with the local physical conditions, hence with the disk region

Spectrally-resolved UV photodesorption of CH4 in pure and layered ices

Context. Methane is among the main components of the ice mantles of insterstellar dust grains, where it is at the start of a rich solid-phase chemical network. Quantification of the photon-induced desorption yield of these frozen molecules and understanding of the underlying processes is necessary to accurately model the observations and the chemical evolution of various regions of the interstellar medium. Aims. This study aims at experimentally determining absolute photodesorption yields for the CH4 molecule as a function of photon energy. The influence of the ice composition is also investigated. By studying the methane desorption from layered CH4:CO ice, indirect desorption processes triggered by the excitation of the CO molecules is monitored and quantified. Methods. Tunable monochromatic VUV light from the DESIRS beamline of the SOLEIL synchrotron is used in the 7 - 13.6 eV (177 - 91 nm) range to irradiate pure CH4 or layers of CH4 deposited on top of CO ice samples. The release of species in the gas phase is monitored by quadrupole mass spectrometry and absolute photodesorption yields of intact CH4 are deduced. Results. CH4 photodesorbs for photon energies higher than ~9.1 eV (~136 nm). The photodesorption spectrum follows the absorption spectrum of CH4, which confirms a desorption mechanism mediated by electronic transitions in the ice. When it is deposited on top of CO, CH4 desorbs between 8 and 9 eV with a pattern characteristic of CO absorption, indicating desorption induced by energy transfer from CO molecules. Conclusions. The photodesorption of CH4 from the pure ice in various interstellar environments is around 2.0 x 10^-3 molecules per incident photon. Results on CO-induced indirect desorption of CH4 provide useful insights for the generalization of this process to other molecules co-existing with CO in ice mantles

Electronic sculpting of ligand-GPCR subtype selectivity:the case of angiotensin II

GPCR subtypes possess distinct functional and pharmacological profiles, and thus development of subtype-selective ligands has immense therapeutic potential. This is especially the case for the angiotensin receptor subtypes AT1R and AT2R, where a functional negative control has been described and AT2R activation highlighted as an important cancer drug target. We describe a strategy to fine-tune ligand selectivity for the AT2R/AT1R subtypes through electronic control of ligand aromatic-prolyl interactions. Through this strategy an AT2R high affinity (<i>K</i>_i = 3 nM) agonist analogue that exerted 18,000-fold higher selectivity for AT2R versus AT1R was obtained. We show that this compound is a negative regulator of AT1R signaling since it is able to inhibit MCF-7 breast carcinoma cellular proliferation in the low nanomolar range

Oscillator strengths for transitions to Rydberg levels in 12C16O^{12}C^{16}O, 13C16O^{13}C^{16}O and 13C18O^{13}C^{18}O between 967 and 972 A

Absorption oscillator strengths have been determined from high-resolution spectra in the 967-972 \AA region of three CO isotopomers for transitions to the Rydberg levels 4{\it p$\pi$}(0), 3{\it d$\pi$}(1) and 4{\it p$\sigma$}(0), as well as to the mixed {\it E(6)} level recently characterized by Eidelsberg et al. (2004). Synchrotron radiation from the Super-ACO electron storage ring at Orsay (LURE) was used as a light source. Oscillator strengths were extracted from the recorded spectra by least-squares fitting of the experimental profiles with synthetic spectra taking into account the homogeneous and heterogeneous interactions of the four levels. Column densities were derived from fits to the 3{\it p$\pi$}(0) absorption band whose oscillator strength is well established. These are the first reported measurements for $^{13}$C$^{18}$O. For $^{12}$C$^{16}$O, our results are consistent with the larger values obtained in the most recent laboratory and astronomical studies.Comment: 9 pages 7 figures 3 tables. Accepted in A&A, date of acceptance 11/05/200

Experimental evidence for water formation on interstellar dust grains by hydrogen and oxygen atoms

Context. The synthesis of water is one necessary step in the origin and development of life. It is believed that pristine water is formed and grows on the surface of icy dust grains in dark interstellar clouds. Until now, there has been no experimental evidence whether this scenario is feasible or not on an astrophysically relevant template and by hydrogen and oxygen atom reactions. Aims. We present here the first experimental evidence of water synthesis by such a process on a realistic grain surface analogue in dense clouds, i.e., amorphous water ice. Methods. Atomic beams of oxygen and deuterium are aimed at a porous water ice substrate (H2O) held at 10 K. Products are analyzed by the temperature-programmed desorption technique. Results. We observe production of HDO and D2O, indicating that water is formed under conditions of the dense interstellar medium from hydrogen and oxygen atoms. This experiment opens up the field of a little explored complex chemistry that could occur on dust grains, believed to be the site where key processes lead to the molecular diversity and complexity observed in the Universe.Comment: 8 pages, 2 figures, 1 table. Submitted to A&