Gas phase formation of the prebiotic molecule formamide: insights from new quantum computations

New insights into the formation of interstellar formamide, a species of great relevance in prebiotic chemistry, are provided by electronic structure and kinetic calculations for the reaction NH2 + H2CO -> NH2CHO + H. Contrarily to what previously suggested, this reaction is essentially barrierless and can, therefore, occur under the low temperature conditions of interstellar objects thus providing a facile formation route of formamide. The rate coefficient parameters for the reaction channel leading to NH2CHO + H have been calculated to be A = 2.6x10^{-12} cm^3 s^{-1}, beta = -2.1 and gamma = 26.9 K in the range of temperatures 10-300 K. Including these new kinetic data in a refined astrochemical model, we show that the proposed mechanism can well reproduce the abundances of formamide observed in two very different interstellar objects: the cold envelope of the Sun-like protostar IRAS16293-2422 and the molecular shock L1157-B2. Therefore, the major conclusion of this Letter is that there is no need to invoke grain-surface chemistry to explain the presence of formamide provided that its precursors, NH2 and H2CO, are available in the gas-phase.Comment: MNRAS Letters, in pres

Properties of nonaqueous electrolytes Quarterly report, 20 Sep. - 19 Dec. 1966

Vapor phase chromatographic analysis of dimethyl formamide, and physical properties of electrolytes containing lithium chloride and/or aluminum chlorid

Dissociative electron attachment to formamide

Formamide (HCONH2) is the smallest molecule with a peptide bond and has recently been observed in the interstellar medium (ISM), suggesting that it may be ubiquitous in star-forming regions. There is therefore considerable interest in the mechanisms by which this molecule may form. One method is electron induced chemistry within the icy mantles on the surface of dust grains. In particular it has been recently shown that functional group dependence exists in electron attachment processes giving rise to site selective fragmentation of molecules at the C-H, O-H and N-H bonds at energies well beyond the threshold for the breaking of any of these bonds allowing novel forms of chemistry that have little or no activation barriers, such as are necessary in the ISM. In this poster we present the results of resent studies on dissociative electron attachment (DEA) to formamide DEA using an improved version of a Velocity Map Imaging (VMI) spectrometer comprised of a magnetically collimated and low energy pulsed electron gun, a Faraday cup (to measure the incident current), an effusive molecular beam, a pulsed field ion extraction, a time of flight analyzer and a two-dimensional position sensitive detector consisting of microchannel plate and a phosphor screen. The VMI spectrometer measures the kinetic energy and angular distribution of the fragment anions produced in the dissociative electron attachment process. The kinetic energy measurements provide information on the internal energies of the fragment anions and determine the dissociation limits of the parent negative ion resonant states responsible for the dissociative electron attachment process. The angular distribution measurements provide the information about the symmetry of these negative ion resonant states. We shall present the details, results and conclusions of these measurements during the conference

Complex organic molecules in comets C/2012 F6 (Lemmon) and C/2013 R1 (Lovejoy): detection of ethylene glycol and formamide

A spectral survey in the 1 mm wavelength range was undertaken in the long-period comets C/2012 F6 (Lemmon) and C/2013 R1 (Lovejoy) using the 30 m telescope of the Institut de radioastronomie millim\'etrique (IRAM) in April and November-December 2013. We report the detection of ethylene glycol (CH$_2$OH)$_2$ (aGg' conformer) and formamide (NH$_2$CHO) in the two comets. The abundances relative to water of ethylene glycol and formamide are 0.2-0.3% and 0.02% in the two comets, similar to the values measured in comet C/1995 O1 (Hale-Bopp). We also report the detection of HCOOH and CH$_3$CHO in comet C/2013 R1 (Lovejoy), and a search for other complex species (methyl formate, glycolaldehyde).Comment: Accepted for publication as a Letter in Astronomy and Astrophysic

New quantum chemical computations of formamide deuteration support a gas-phase formation of this prebiotic molecule

Based on recent work, formamide might be a potentially very important molecule in the emergence of terrestrial life. Although detected in the interstellar medium for decades, its formation route is still debated, whether in the gas phase or on the dust grain surfaces. Molecular deuteration has proven to be, in other cases, an efficient way to identify how a molecule is synthesised. For formamide, new published observations towards the IRAS16293-2422 B hot corino show that its three deuterated forms have all the same deuteration ratio, 2--5%, and that this is a factor 3--8 smaller than that measured for H2CO towards the IRAS16293-2422 protostar. Following a previous work on the gas-phase formamide formation via the reaction NH2 + H2CO -> HCONH2 + H, we present here new calculations of the rate coefficients for the production of monodeuterated formamide through the same reaction, starting from monodeuterated NH2 or H2CO. Some misconceptions regarding our previous treatment of the reaction are also cleared up. The results of the new computations show that, at the 100 K temperature of the hot corino, the rate of deuteration of the three forms is the same, within 20%. On the contrary, the reaction between non-deuterated species proceeds three times faster than that with deuterated ones. These results confirm that a gas-phase route for the formation of formamide is perfectly in agreement with the available observations.Comment: MNRAS in pres

Adhesion attenuation and enhancement in aqueous solutions

When two surfaces confine water layers between them at the nanoscale, the behaviour of these confined water molecules can deviate significantly from the behaviour of bulk water, and it could reflect on the adhesion of such surfaces. This study assesses the role of confined water layers on the adhesion of hydrophilic surfaces and how sensitive this adhesion is to the presence of contaminants. Our methodology used atomic force microscopy adhesion measurements, whereby an alumina-sputtered sphere-tipped cantilever was interacted versus a flat alumina single crystal. Testing was performed under immersed conditions using (i) water, (ii) water/dimethylformamide mixtures, (iii) water/ethanol mixtures, and (iv) water/formamide mixtures. These solutions were intended to assess the influence of dielectric constant, molecule size, and the number of hydrogen bonding opportunities available to molecules upon confinement between surfaces. It was found that dilute concentrations of ethanol and formamide decreased the adhesion. In contrast, the adhesion increased in the presence of dilute concentrations of dimethylformamide. The adhesion was attenuated by in excess of two orders of magnitude for high concentrations of the organic solutes

Molecules with a peptide link in protostellar shocks: a comprehensive study of L1157

Interstellar molecules with a peptide link -NH-C(=O)-, like formamide (NH$_2$CHO), acetamide (NH$_2$COCH$_3$) and isocyanic acid (HNCO) are particularly interesting for their potential role in pre-biotic chemistry. We have studied their emission in the protostellar shock regions L1157-B1 and L1157-B2, with the IRAM 30m telescope, as part of the ASAI Large Program. Analysis of the line profiles shows that the emission arises from the outflow cavities associated with B1 and B2. Molecular abundance of $\approx~(0.4-1.1)\times 10^{-8}$ and $(3.3-8.8)\times 10^{-8}$ are derived for formamide and isocyanic acid, respectively, from a simple rotational diagram analysis. Conversely, NH$_2$COCH$_3$ was not detected down to a relative abundance of a few $\leq 10^{-10}$. B1 and B2 appear to be among the richest Galactic sources of HNCO and NH$_2$CHO molecules. A tight linear correlation between their abundances is observed, suggesting that the two species are chemically related. Comparison with astrochemical models favours molecule formation on ice grain mantles, with NH$_2$CHO generated from hydrogenation of HNCO.Comment: 11 pages, 9 figures. Accepted for publication in MNRAS Main Journal. Accepted 2014 August 19, in original form 2014 July

Shedding light on the formation of the pre-biotic molecule formamide with ASAI

Formamide (NH2CHO) has been proposed as a pre-biotic precursor with a key role in the emergence of life on Earth. While this molecule has been observed in space, most of its detections correspond to high-mass star-forming regions. Motivated by this lack of investigation in the low-mass regime, we searched for formamide, as well as isocyanic acid (HNCO), in 10 low- and intermediate-mass pre-stellar and protostellar objects. The present work is part of the IRAM Large Programme ASAI (Astrochemical Surveys At IRAM), which makes use of unbiased broadband spectral surveys at millimetre wavelengths. We detected HNCO in all the sources and NH2CHO in five of them. We derived their abundances and analysed them together with those reported in the literature for high-mass sources. For those sources with formamide detection, we found a tight and almost linear correlation between HNCO and NH2CHO abundances, with their ratio being roughly constant -between 3 and 10- across 6 orders of magnitude in luminosity. This suggests the two species are chemically related. The sources without formamide detection, which are also the coldest and devoid of hot corinos, fall well off the correlation, displaying a much larger amount of HNCO relative to NH2CHO. Our results suggest that, while HNCO can be formed in the gas phase during the cold stages of star formation, NH2CHO forms most efficiently on the mantles of dust grains at these temperatures, where it remains frozen until the temperature rises enough to sublimate the icy grain mantles. We propose hydrogenation of HNCO as a likely formation route leading to NH2CHO.Comment: 26 pages, 9 figures. Accepted by Monthly Notices of the Royal Astronomical Societ

Can re-entrance be observed in force induced transitions?

A large conformational change in the reaction co-ordinate and the role of the solvent in the formation of base-pairing are combined to settle a long standing issue {\it i.e.} prediction of re-entrance in the force induced transition of DNA. A direct way to observe the re-entrance, i.e a strand goes to the closed state from the open state and again to the open state with temperature, appears difficult to be achieved in the laboratory. An experimental protocol (in direct way) in the constant force ensemble is being proposed for the first time that will enable the observation of the re-entrance behavior in the force-temperature plane. Our exact results for small oligonucleotide that forms a hairpin structure provide the evidence that re-entrance can be observed.Comment: 12 pages and 5 figures (RevTex4). Accepted in Europhys Lett. (2009