scholarly journals Formation of interstellar cyanoacetamide: a rotational and computational study

2020 ◽  
Vol 644 ◽  
pp. A3
Author(s):  
M. Sanz-Novo ◽  
I. León ◽  
J. L. Alonso ◽  
A. Largo ◽  
C. Barrientos
Keyword(s):  
Interstellar Medium ◽  
Formation Process ◽  
Activation Barrier ◽  
Computational Study ◽  
High Energy ◽  
Spectroscopic Technique ◽  
Spectroscopic Constants ◽  
Phase Reaction ◽  
Neutral Form ◽  
High Level

Context. Cyanoacetamide is a –CN bearing molecule that is also an amide derivative target molecule in the interstellar medium. Aims. The aim of our investigation is to analyze the feasibility of a plausible formation process of protonated cyanoacetamide under interstellar conditions and to provide direct experimental frequencies of the ground vibrational state of the neutral form in the microwave region in order to enable its eventual identification in the interstellar medium. Methods. We used high-level theoretical computations to study the formation process of protonated cyanoacetamide. Furthermore, we employed a high-resolution laser-ablation molecular beam Fourier transform spectroscopic technique to measure the frequencies of the neutral form. Results. We report the first rotational characterization of cyanoacetamide, and a precise set of the relevant rotational spectroscopic constants have been determined as a first step to identifying the molecule in the interstellar medium. We fully explored the potential energy surface to study a gas-phase reaction on the formation process of protonated cyanoacetamide. We found that an exothermic process with no net activation barrier is initiated by the high-energy isomer of protonated hydroxylamine, which leads to protonated cyanoacetamide.

scholarly journals Accurate rest frequencies for propargylamine in the ground and low-lying vibrational states

2018 ◽  
Vol 615 ◽  
pp. A176 ◽  
Author(s):  
C. Degli Esposti ◽  
L. Dore ◽  
C. Puzzarini ◽  
M. Biczysko ◽  
J. Bloino ◽  
...  
Keyword(s):  
Interstellar Medium ◽  
Organic Molecules ◽  
Coupling Constants ◽  
Spectroscopic Constants ◽  
Rotational Spectrum ◽  
Centrifugal Distortion ◽  
Vibrational States ◽  
Important Species ◽  
Centrifugal Distortion Constants ◽  
High Level

Context. To date, several complex organic molecules have been detected in the interstellar medium, and they have been suggested as precursors of biologically important species. Propargylamine (HC ≡C−CH2−NH2) is structurally similar to a number of other organic molecules which have already been identified by radioastronomy, making it a good candidate for astrophysical detection. Aims. This work provides accurate rest frequencies of propargylamine, from the centimeter-wave to the submillimeter-wave region, useful to facilitate the detection of this molecule in the interstellar medium. Methods. An extensive laboratory study of the rotational spectrum of propargylamine has been performed using a pulsed-jet Fourier Transform Microwave (FTMW) spectrometer (7–19 GHz frequency range) and a frequency modulation microwave spectrometer (75–560 GHz). Several hundred rotational transitions of propargylamine were recorded in the ground and three lowest excited vibrational states. The experiments were supported by high-level ab initio computations, mainly employed to characterize the vibrational state structure and to predict spectroscopic parameters unknown prior to this study. Results. The measured transition frequencies yielded accurate rotational constants and the complete sets of quartic and sextic centrifugal distortion constants for propargylamine in its vibrational ground state. 14N-nuclear quadrupole coupling constants were also determined. Rotational and quartic centrifugal distortion constants were also obtained for the low-lying excited states v13 = 1 (A′), v20 = 1 (A″), and v21 = 1 (A″). The a-type Coriolis resonance which couples the v13 = 1 and v21 = 1 levels was analyzed. Conclusions. The determined spectroscopic constants allowed for the compilation of a dataset of highly accurate rest frequencies for astrophysical purposes in the millimeter and submillimeter regions with 1σ uncertainties that are smaller than 0.050 MHz, corresponding to 0.03 km s−1 at 500 GHz in radial equivalent velocity.

scholarly journals Fate of the Gas-Phase Reaction Between Oxirane and the CN Radical in Interstellar Conditions

2021 ◽  
Vol 8 ◽  
Author(s):  
Silvia Alessandrini ◽  
Mattia Melosso
Keyword(s):  
Interstellar Medium ◽  
Density Functional ◽  
Reaction Pathway ◽  
High Energy ◽  
Main Reaction ◽  
Molecular Formula ◽  
Phase Reaction ◽  
Complex Molecules ◽  
High Energy Barrier ◽  
Potential Formation

The escalating identification of new complex molecules in the interstellar medium claims for potential formation routes of such species. In this regard, the present work considers the reaction between oxirane and the CN radical as a feasible formation mechanism of species having the C3H3NO molecular formula. Indeed, the compounds of this family are elusive in the interstellar medium and suggestions on which species could be formed at low temperature and low pressure conditions might aid their discovery. The c-C2H4O + CN reaction has been investigated from the thermodynamic and kinetic points of view. The thermodynamic has been studied by means of a double-hybrid density functional and revealed the presence of several mechanisms submerged with respect to the reactants energy, with the potential formation of oxazole and cyanoacetaldehyde. However, the kinetic results suggest that the main reaction pathway is the H-extraction, leading to 2-oxiranyl radical and HCN. The formation of cyanoacetaldehyde + H and of H2CCN + H2CO is also possible with smaller rate constants, while the production of oxazole is negligible due to the presence of a high energy barrier.

scholarly journals Anharmonic Vibrational Frequencies and Spectroscopic Constants for the Detection of Ethynol in Space

2021 ◽  
Vol 7 ◽  
Author(s):  
Jax D. Dallas ◽  
Brent R. Westbrook ◽  
Ryan C. Fortenberry
Keyword(s):  
Interstellar Medium ◽  
Organic Molecules ◽  
Building Blocks ◽  
Spectroscopic Constants ◽  
Simultaneous Formation ◽  
Water Ice ◽  
Molecular Building Blocks ◽  
High Level ◽  
Complex Organic ◽  
Quantum Chemical Computations

The ethynol (HCCOH) molecule has recently been shown to be present in simulated astrochemical ices possibly linking it to molecular building blocks for interstellar complex organic molecules like amino acids. The proposed reaction mechanism suggests the simultaneous formation of both ketene and ethynol from mixed carbon monoxide/water ice in simulated interstellar conditions. Rigorous anharmonic spectral data within both the IR and microwave regions are needed for possible detection of ethynol in the interstellar medium. This study provides the first such data for this molecule from high-level quantum chemical computations where experiment is currently lacking. Ethynol has a Beff comparable to, but distinct from acetonitrile at 9,652.1 MHz and three notable infrared features with two in the hydride stretching-regions and the C–C stretch at 2,212.8 cm−1. The ketene isomer has already been detected in the interstellar medium, and the possible detection of ethynol made possible by this work may lead to a deeper understanding of the proposed ice formation mechanism involving both species and how this relates to the molecular origins of life.

scholarly journals A computational study for the reaction mechanism of metal-free cyanomethylation of aryl alkynoates with acetonitrile

RSC Advances ◽  
2021 ◽  
Vol 11 (30) ◽  
pp. 18246-18251
Author(s):  
Selçuk Eşsiz
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Density Functional ◽  
Computational Study ◽  
Coupled Cluster ◽  
Functional Theory ◽  
Metal Free ◽  
Coupled Cluster Methods ◽  
High Level ◽  
Cluster Methods

A computational study of metal-free cyanomethylation and cyclization of aryl alkynoates with acetonitrile is carried out employing density functional theory and high-level coupled-cluster methods, such as [CCSD(T)].

scholarly journals Density Functional Theory and Complete Basis Set Ab Initio Computational Study of Five-, Six-, Seven- and Eight-hydrogen Coordinated Carbon Cations

1999 ◽  
Vol 23 (8) ◽  
pp. 502-503
Author(s):  
Branko S. Jursic
Keyword(s):  
Density Functional Theory ◽  
Ab Initio ◽  
Density Functional ◽  
Computational Study ◽  
Basis Set ◽  
Functional Theory ◽  
Complete Basis ◽  
Complete Basis Set ◽  
High Level

High level ab initio and density functional theory studies are performed on highly protonated methane species.

scholarly journals The interstellar medium in young supernova remnants: key to the production of cosmic X-rays and $\gamma $-rays

2021 ◽  
Vol 366 (6) ◽  
Author(s):  
Hidetoshi Sano ◽  
Yasuo Fukui
Keyword(s):  
Interstellar Medium ◽  
Supernova Remnants ◽  
Cosmic Ray ◽  
High Energy ◽  
X Rays ◽  
Interstellar Gas ◽  
High Energy Radiation ◽  
Dense Cores ◽  
The Relationship ◽  
Turbulent Velocity Field

AbstractWe review recent progress in elucidating the relationship between high-energy radiation and the interstellar medium (ISM) in young supernova remnants (SNRs) with ages of ∼2000 yr, focusing in particular on RX J1713.7−3946 and RCW 86. Both SNRs emit strong nonthermal X-rays and TeV $\gamma $ γ -rays, and they contain clumpy distributions of interstellar gas that includes both atomic and molecular hydrogen. We find that shock–cloud interactions provide a viable explanation for the spatial correlation between the X-rays and ISM. In these interactions, the supernova shocks hit the typically pc-scale dense cores, generating a highly turbulent velocity field that amplifies the magnetic field up to 0.1–1 mG. This amplification leads to enhanced nonthermal synchrotron emission around the clumps, whereas the cosmic-ray electrons do not penetrate the clumps. Accordingly, the nonthermal X-rays exhibit a spatial distribution similar to that of the ISM on the pc scale, while they are anticorrelated at sub-pc scales. These results predict that hadronic $\gamma $ γ -rays can be emitted from the dense cores, resulting in a spatial correspondence between the $\gamma $ γ -rays and the ISM. The current pc-scale resolution of $\gamma $ γ -ray observations is too low to resolve this correspondence. Future $\gamma $ γ -ray observations with the Cherenkov Telescope Array will be able to resolve the sub-pc-scale $\gamma $ γ -ray distribution and provide clues to the origin of these cosmic $\gamma $ γ -rays.

A computational study on the gas phase reaction of Os+ with N2O

2009 ◽  
Vol 20 (8) ◽  
pp. 1010-1014 ◽  
Author(s):  
Tao Hong Li ◽  
Chuan Ming Wang ◽  
Shi Wen Yu ◽  
Xiang Yi Liu ◽  
Hui Fu ◽  
...  
Keyword(s):  
Gas Phase ◽  
Computational Study ◽  
Phase Reaction ◽  
Gas Phase Reaction

Activation barriers for oxygen diffusion in polystyrene and polycarbonate glasses: effects of codissolved argon, helium, and nitrogen

1995 ◽  
Vol 73 (11) ◽  
pp. 1831-1840 ◽  
Author(s):  
Bojie Wang ◽  
Peter R. Ogilby
Keyword(s):  
Diffusion Coefficient ◽  
Polymer Matrix ◽  
Diffusion Coefficients ◽  
Oxygen Diffusion ◽  
Arrhenius Plot ◽  
Activation Barrier ◽  
Spectroscopic Technique ◽  
Activation Barriers ◽  
Data Yield ◽  
Diffusion Activation

A recently developed spectroscopic technique was used to determine oxygen diffusion coefficients as a function of temperature for polystyrene and polycarbonate films. Data were recorded at total pressures <300 Torr over the temperature range 5–45 °C under conditions in which argon, helium, and nitrogen, respectively, were copenetrants. In all cases, the presence of the additional gas caused an increase in the oxygen diffusion coefficient. Arrhenius plots of the data yield (a) a diffusion activation barrier, Eact, and (b) a diffusion coefficient, D0, that represents the condition of "barrier-free" gas transport for the temperature domain over which the Arrhenius plot is linear. For all cases examined in both polystyrene and polycarbonate, D0 increased with an increase in the partial pressure of added gas. In polystyrene, the presence of an additional gas did not change Eact. In polycarbonate, Eact obtained in the presence of helium and argon likewise did not differ from that obtained in the absence of the copenetrant. When nitrogen was the added gas, however, a larger value of Eact was obtained. This latter observation is interpreted to reflect the plasticization of polycarbonate by nitrogen. Eact and D0 data are discussed within the context of a model that distinguishes between dynamic and static elements of free volume in the polymer matrix. Keywords: oxygen diffusion, polystyrene, polycarbonate, activation barrier.

On sinterability of nanostructured W produced by high-energy ball milling

2007 ◽  
Vol 22 (5) ◽  
pp. 1200-1206 ◽  
Author(s):  
R. Malewar ◽  
K.S. Kumar ◽  
B.S. Murty ◽  
B. Sarma ◽  
S.K. Pabi
Keyword(s):  
Sintered Density ◽  
Sintering Temperature ◽  
High Energy ◽  
Deformation Bands ◽  
Dramatic Decrease ◽  
Powder Charge ◽  
Grinding Media ◽  
Energy Ball ◽  
High Level ◽  
First Time

The present investigation reports for the first time a dramatic decrease in the sintering temperature of elemental W from the conventional temperature of ≥2500 °C to the modest temperature range of 1700–1790 °C by making the W powder nanostructured through high-energy mechanical milling (MM) prior to sintering. The crystallite size of the initial W powder charge with a particle size of 3–4 μm could be brought down to 8 nm by MM for 5 h in WC grinding media. Further milling resulted in a high level of WC contamination, which apparently was due to work hardening and the grain refinement of W. A sintered density as high as 97.4% was achieved by sintering cold, isostatically pressed nanocrystalline (8 nm) W powder at 1790 °C for 900 min. The microstructure of the sintered rods showed the presence of deformation bands, but no cracks, within a large number of W grains. The mechanical properties, when compared with the hardness and elastic modulus, of the sintered nano-W specimen were somewhat superior to those reported for the conventional sintered W.

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