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

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

Density fluctuations and single-particle dynamics in liquid lithium

The single-particle and collective dynamical properties of liquid lithium have been evaluated at several thermodynamic states near the triple point. This is performed within the framework of mode-coupling theory, using a self-consistent scheme which, starting from the known static structure of the liquid, allows the theoretical calculation of several dynamical properties. Special attention is devoted to several aspects of the single-particle dynamics, which are discussed as a function of the thermodynamic state. The results are compared with those of Molecular Dynamics simulations and other theoretical approaches.Comment: 31 pages (in preprint format), 14 figures. Submitted to Phys. Rev.

Quantum chemical computations of gas-phase glycolaldehyde deuteration and constraints to its formation route

Despite the detection of numerous interstellar complex organic molecules (iCOMs) for decades, it is still a matter of debate whether they are synthesized in the gas-phase or on the icy surface of interstellar grains. In the past, molecular deuteration has been used to constrain the formation paths of small and abundant hydrogenated interstellar species. More recently, the deuteration degree of formamide, one of the most interesting iCOM, has also been explained in the hypothesis that it is formed by the gas-phase reaction NH$_2$ + H$_2$CO. In this article, we aim at using molecular deuteration to constrain the formation of another iCOM, glycolaldehyde, which is an important prebiotic species. More specifically, we have performed dedicated electronic structure and kinetic calculations to establish the glycolaldehyde deuteration degree in relation to that of ethanol, which is its possible parent species according to the suggestion of Skouteris et al. (2018). We found that the abundance ratio of the species containing one D-atom over the all-protium counterpart depends on the produced D isotopomer and varies from 0.9 to 0.5. These theoretical predictions compare extremely well with the monodeuterated isotopomers of glycolaldehyde and that of ethanol measured towards the Solar-like protostar IRAS 16293-2422, supporting the hypothesis that glycolaldehyde could be produced in the gas-phase for this source. In addition, the present work confirms that the deuterium fractionation of iCOMs cannot be simply anticipated based on the deuterium fractionation of the parent species but necessitates a specific study, as already shown for the case of formamide.Comment: Accepted by Ap

Fluctuating magnetic moments in liquid metals

We re-analyze literature data on neutron scattering by liquid metals to show that non-magnetic liquid metals possess a magnetic moment that fluctuates on a picosecond time scale. This time scale follows the motion of the cage-diffusion process in which an ion rattles around in the cage formed by its neighbors. We find that these fluctuating magnetic moments are present in liquid Hg, Al, Ga and Pb, and possibly also in the alkali metals.Comment: 17 pages, 5 figures, submitted to PR

Phonon-like and single particle dynamics in liquid lithium

The dynamic structure factor, S(Q,E), of liquid lithium (T=475 K) has been determined by inelastic x-ray scattering (IXS) in the momentum transfer region (Q = 1.4-110 nm-1). These data allow to observe how, in a simple liquid, a phonon-like collective mode evolves towards the single particle dynamics. As a function of Q, one finds: i) at low Q's, a sound mode with a positive dispersion of the sound velocity, ii) at intermediate Q's, excitations whose energy oscillates similarly to phonons in the crystal Brillouin zones, and iii) at high Q's, the S(Q,E) approaches a Gaussian shape, indicating that the single particle dynamics has been reached.Comment: 3 pages and 5 figure

Inelastic X-ray scattering study of the collective dynamics in liquid sodium

Inelastic X-ray scattering data have been collected for liquid sodium at T=390 K, i.e. slightly above the melting point. Owing to the very high instrumental resolution, pushed up to 1.5 meV, it has been possible to determine accurately the dynamic structure factor, $S(Q,\omega)$, in a wide wavevector range, $1.5 \div 15$ nm$^{-1}$, and to investigate on the dynamical processes underlying the collective dynamics. A detailed analysis of the lineshape of $S(Q,\omega)$, similarly to other liquid metals, reveals the co-existence of two different relaxation processes with slow and fast characteristic timescales respectively. The present data lead to the conclusion that: i) the picture of the relaxation mechanism based on a simple viscoelastic model fails; ii) although the comparison with other liquid metals reveals similar behavior, the data do not exhibit an exact scaling law as the principle of corresponding state would predict.Comment: RevTex, 7 pages, 6 eps figures. Accepted by Phys. Rev.

Simple theory for spin-lattice relaxation in metallic rare earth ferromagnets

The spin-lattice relaxation time $\tau_{SL}$ is a key quantity both for the dynamical response of ferromagnets excited by laser pulses and as the speed limit of magneto-optical recording. Extending the theory for the electron paramagnetic resonance of magnetic impurities to spin-lattice relaxation in ferromagnetic rare earths we calculate $\tau_{SL}$ for Gd and find a value of 48 ps in very good agreement with time-resolved spin-polarized photoemission experiments. We argue that the time scale for $\tau_{SL}$ in metals is essentially given by the spin-orbit induced magnetocrystalline anisotropy energy.Comment: 18 pages revtex, 5 uuencoded figure

The census of interstellar complex organic molecules in the Class I hot corino of SVS13-A

We present the first census of the interstellar Complex Organic Molecules (iCOMs) in the low-mass Class I protostar SVS13-A, obtained by analysing data from the IRAM-30m Large Project ASAI (Astrochemical Surveys At IRAM). They consist of an high-sensitivity unbiased spectral survey at the 1mm, 2mm and 3mm IRAM bands. We detected five iCOMs: acetaldehyde (CH$_3$CHO), methyl formate (HCOOCH$_3$), dimethyl ether (CH$_3$OCH$_3$), ethanol (CH$_3$CH$_2$OH) and formamide (NH$_2$CHO). In addition we searched for other iCOMs and ketene (H$_2$CCO), formic acid (HCOOH) and methoxy (CH$_3$O), whose only ketene was detected. The numerous detected lines, from 5 to 37 depending on the species, cover a large upper level energy range, between 15 and 254 K. This allowed us to carry out a rotational diagram analysis and derive rotational temperatures between 35 and 110 K, and column densities between $3\times 10^{15}$ and $1\times 10^{17}$ cm$^{-2}$ on the 0."3 size previously determined by interferometric observations of glycolaldehyde. These new observations clearly demonstrate the presence of a rich chemistry in the hot corino towards SVS13-A. The measured iCOMs abundances were compared to other Class 0 and I hot corinos, as well as comets, previously published in the literature. We find evidence that (i) SVS13-A is as chemically rich as younger Class 0 protostars, and (ii) the iCOMs relative abundances do not substantially evolve during the protostellar phase.Comment: 24 pages, MNRAS in pres

Two liquid states of matter: A new dynamic line on a phase diagram

It is generally agreed that the supercritical region of a liquid consists of one single state (supercritical fluid). On the other hand, we show here that liquids in this region exist in two qualitatively different states: "rigid" and "non-rigid" liquid. Rigid to non-rigid transition corresponds to the condition {\tau} ~ {\tau}0, where {\tau}is liquid relaxation time and {\tau}0 is the minimal period of transverse quasi-harmonic waves. This condition defines a new dynamic line on the phase diagram, and corresponds to the loss of shear stiffness of a liquid at all available frequencies, and consequently to the qualitative change of many important liquid properties. We analyze the dynamic line theoretically as well as in real and model liquids, and show that the transition corresponds to the disappearance of high-frequency sound, qualitative changes of diffusion and viscous flow, increase of particle thermal speed to half of the speed of sound and reduction of the constant volume specific heat to 2kB per particle. In contrast to the Widom line that exists near the critical point only, the new dynamic line is universal: it separates two liquid states at arbitrarily high pressure and temperature, and exists in systems where liquid - gas transition and the critical point are absent overall.Comment: 21 pages, 8 figure