56 research outputs found
Twisted Intramolecular Charge Transfer in Protonated Amino Pyridine
International audienceThe excited state properties of protonated ortho (2-), meta (3-) and para (4-) aminopyridine molecules have been investigated through UV photo fragmentation spectroscopy and excited state couple cluster CC2 calculations. Cryogenic ion spectroscopy allows recording well-resolved vibronic spectroscopy that can be nicely reproduced through Franck Condon simulations of the pp* local minimum of the excited state potential energy surface. The excited state lifetimes have also been measured through a pump-probe excitation scheme and compared to the estimated radiative lifetimes. Although protonated aminopyridines are rather simple aromatic molecules, their deactivation mechanisms are indeed quite complex with unexpected results. In protonated 3-and 4-aminopyridine, the fragmentation yield is negligible around the band origin, which implies the absence of internal conversion to the ground state. Besides, a twisted intramolecular charge transfer reaction is evidenced in protonated 4-aminopyridine around the band origin, while excited state proton transfer from the pyridinic nitrogen to the adjacent carbon atom opens with roughly 500 cm-1 of excess energy
Hydrogenation of solid hydrogen cyanide HCN and methanimine CH2NH at low temperature
International audienceContext. Hydrogenation reactions dominate grain surface chemistry in dense molecular clouds and lead to the formation of complex saturated molecules in the interstellar medium. Aims. We investigate in the laboratory the hydrogenation reaction network of hydrogen cyanide HCN. Methods. Pure hydrogen cyanide HCN and methanimine CH2NH ices are bombarded at room temperature by H-atoms in an ultra-high vacuum experiment. Warm H-atoms are generated in an H2 plasma source. The ices are monitored with Fourier-transform infrared spectroscopy in reflection absorption mode. The hydrogenation products are detected in the gas phase by mass spectroscopy during temperature-programmed desorption experiments. Results. HCN hydrogenation leads to the formation of methylamine CH3NH2, and CH2NH hydrogenation leads to the formation of methylamine CH3NH2, suggesting that CH2NH can be a hydrogenation-intermediate species between HCN and CH3NH2. Conclusions. In cold environments the HCN hydrogenation reaction can produce CH3NH2, which is known to be a glycine precursor, and to destroy solid-state HCN, preventing its observation in molecular clouds ices
Identification of Large Equivalent Width Dusty Galaxies at 4 z 6 from Sub-mm Colours
Infrared (IR), sub-millimetre (sub-mm) and millimetre (mm) databases contain
a huge quantity of high quality data. However, a large part of these data are
photometric, and are thought not to be useful to derive a quantitative
information on the nebular emission of galaxies. The aim of this project is
first to identify galaxies at z > 4-6, and in the epoch of reionization from
their sub-mm colours. We also aim at showing that the colours can be used to
try and derive physical constraints from photometric bands, when accounting for
the contribution from the IR fine structure lines to these photometric bands.
We model the flux of IR fine structure lines with CLOUDY, and add them to the
dust continuum emission with CIGALE. Including or not emission lines in the
simulated spectral energy distribution (SED) modifies the broad band emission
and colours. The introduction of the lines allows to identify strong star
forming galaxies at z > 4 - 6 from the log10 (PSW_250um/PMW_350um) versus log10
(LABOCA_870um/PLW_500um) colour-colour diagramme. By comparing the relevant
models to each observed galaxy colour, we are able to roughly estimate the
fluxes of the lines, and the associated nebular parameters. This method allows
to identify a double sequence in a plot built from the ionization parameter and
the gas metallicity. The HII and photodissociation region (PDR) fine structure
lines are an essential part of the SEDs. It is important to add them when
modelling the spectra, especially at z > 4 - 6 where their equivalent widths
can be large. Conversely, we show that we can extract some information on
strong IR fine structure lines and on the physical parameters related to the
nebular emission from IR colour-colour diagrams.Comment: Paper accepted in Astronomy and Astrophysics on 10 November 202
Identification of Ammonium Salts on Comet 67P/C-G Surface from Infrared VIRTIS/Rosetta Data Based on Laboratory Experiments. Implications and Perspectives
The nucleus of comet 67P/Churyumov-Gerasimenko exhibits a broad spectral
reflectance feature around 3.2 m, which is omnipresent in all spectra of
the surface, and whose attribution has remained elusive since its discovery.
Based on laboratory experiments, we have shown that most of this absorption
feature is due to ammonium (NH4+) salts mixed with the dark surface material.
The depth of the band is compatible with semi-volatile ammonium salts being a
major reservoir of nitrogen in the comet, which could dominate over refractory
organic matter and volatile species. These salts may thus represent the
long-sought reservoir of nitrogen in comets, possibly bringing their
nitrogen-to-carbon ratio in agreement with the solar value. Moreover, the
reflectance spectra of several asteroids are compatible with the presence of
NH4+ salts at their surfaces. The presence of such salts, and other
NH4+-bearing compounds on asteroids, comets, and possibly in proto-stellar
environments, suggests that NH4+ may be a tracer of the incorporation and
transformation of nitrogen in ices, minerals and organics, at different phases
of the formation of the Solar System
Electric dipole moments of highly excited molecular vibrational states
In this work, new spectroscopic techniques have been developed to measure electric dipole moments of highly excited rovibrational states of small polyatomic molecules in the gas phase. These techniques make use of lasers arid of microwave synthesizers. They enable one to measure the change on a molecular system caused by applying an external electric field, which is called Stark effect and from this, extract the dipole moment. The first technique, called microwave Stark spectroscopy, makes use of microwave-optical double resonance combined to either laser induced fluorescence or vibrational predissociation detection. The second approach, called Stark induced quantum beat spectroscopy, relies on the time evolution of a coherently prepared molecular wavepacket in an electric field, using either electronic photodissociation or laser induced fluorescence for detection. These techniques have been applied to H2C0, HOCl, HDO, and H20 for whom the electric dipole moment have been measured for several highly excited rovibrational states of the ground electronic state. Using these experimental measurements, the dependence of the dipole moment vector, both in orientation and in magnitude, on the vibrational excitation is discussed. Moreover the experimental data are used to test ab initio calculations potential energy and dipole moment surfaces and to establish critical benchmarks for future improvements. Due to the rarity of dipole moment data for highly excited vibrational states and their central role in transition intensities, intermolecular forces and collisions, these measurements are of special importance for chemical and energy transfer processes in atmospheric sciences, combustion studies, planetology, or more generally in the whole quantitative spectroscopy field, where transitions intensities are at least as important as line frequency positions
Evidence of Surface Catalytic Effect on Cosmic Dust Grain Analogs: The Ammonia and Carbon Dioxide Surface Reaction
International audienceSurface chemistry on cosmic dust grains plays an important role in the formation of molecules at low temperatures in the interstellar and circumstellar environments. For the first time, we experimentally put in evidence the catalytic role of dust surfaces using the thermal reaction CO2 + 2NH3 → {NH}}4}+NH2COO-, which is also a proxy of radical-radical reactions. Nanometer-sized amorphous silicate and carbon grains produced in our laboratory were used as grain analogs. Surface catalysis on grains accelerates the kinetics of the reaction studied at a temperature of 80 K by a factor of up to 3 compared to the reaction occurring in the molecular solid. The evidence of the catalytic effect of grain surfaces opens a door for experiments and calculations on the formation of interstellar and circumstellar molecules on dust. Ammonium carbamate on the surface of grains or released intact into protostellar or protoplanetary disk phases can give start to a network of prebiotic reactions. Therefore, there should be a great interest to search for ammonium carbamate and its daughter molecule, carbamic acid, in interstellar clouds, protostellar envelopes, and protoplanetary disks
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