skip to main content

Title: Mechanisms for gas-phase molecular formation of neutral formaldehyde (H 2 CO) in cold astrophysical regions
Context. Formaldehyde is a potential biogenic precursor involved in prebiotic chemical evolution. The cold conditions of the interstellar medium (ISM) allow H 2 CO to be reactive, playing a significant role as a chemical intermediate in formation pathways leading to interstellar complex organic molecules. However, gas-phase molecular formation mechanisms in cold regions of the ISM are poorly understood. Aims. We computationally determine the most favored gas-phase molecular formation mechanisms at local thermodynamic equilibrium conditions that can produce the detected amounts of H 2 CO in diffuse molecular clouds (DMCs), in dark, cold, and dense molecular clouds (DCDMCs), and in three regions of circumstellar envelopes of low-mass protostars (CELMPs). Methods. The potential energy surfaces, thermodynamic functions, and single-point energies for transition states were calculated at the CCSD(T)-F12/cc-pVTZ-F12 and MP2/aug-cc-pVDZ levels of theory and basis sets. Molecular thermodynamics and related partition functions were obtained by applying the Maxwell-Boltzmann quantum statistics theory from energies computed at CCSD(T)-F12/cc-pVTZ-F12 with corrections for zero-point energy. A literature review on detected abundances of reactants helped us to propose the most favorable formation routes. Results. The most probable reactions that produce H 2 CO in cold astrophysical regions are: 1 CH 2 + ⋅ 3 O 2 → more » 1 H 2 CO + O⋅( 3 P) in DMCs, ⋅ 3 CH 2 + ⋅ 3 O 2 → 1 H 2 CO + ⋅O( 3 P) in DCDMCs, and ⋅CH 3 + ⋅O( 3 P) → 1 H 2 CO + ⋅H in region III, ⋅CH 3 +⋅O( 1 D) → 1 H 2 CO + ⋅H in region II, and 1 CH 2 + ⋅ 3 O 2 → 1 H 2 CO + ⋅O( 3 P) in region I belonging to CELMPs. Conclusions. Quantum chemical calculations suggest that the principal carbonaceous precursors of H 2 CO in cold regions for the gas-phase are CH 2 (a 1 A 1 ), and ⋅CH 2 (X 3 B 1 ) combined with ⋅O 2 ( 3 Σ g ) and ⋅CH 3 ( 2 A ” ) + ⋅O( 3 P) / O( 1 D). Reactions based on more complex reagents yield less effective thermodynamics in the gas-phase H 2 CO molecular formation. « less
; ;
Award ID(s):
Publication Date:
Journal Name:
Astronomy & Astrophysics
Page Range or eLocation-ID:
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Five substituted cyclopropenylidene derivatives (c-C3HX, X=CN, OH, F, NH2), all currently undetected in the interstellar medium (ISM), are found herein to have mechanistically viable, gas-phase formation pathways through neutral–neutral additions of ·X ontoc-C3H2. The detection and predicted formation mechanism ofc-C3HC2H introduces a need for the chemistry ofc-C3H2and any possible derivatives to be more fully explored. Chemically accurate CCSD(T)-F12/cc-pVTZ-F12 calculations provide exothermicities of additions of various radical species toc-C3H2, alongside energies of submerged intermediates that are crossed to result in product formation. Of the novel reaction mechanisms proposed, the addition of the cyano radical is the most exothermic at -16.10 kcal mol−1. All five products are found to or are expected to have at least one means of associating barrierlessly to form a submerged intermediate, a requirement for the cold chemistry of the ISM. The energetically allowed additions arise as a result of the strong electrophilicity of the radical species as well as the product stability gained through substituent-ring conjugation.

  2. The challenges associated with the out-of-plane bending problem in multiply-bonded hydrocarbon molecules can be mitigated in quartic force field analyses by varying the step size in the out-of-plane coordinates. Carbon is a highly prevalent element in astronomical and terrestrial environments, but this major piece of its spectra has eluded theoretical examinations for decades. Earlier explanations for this problem focused on method and basis set issues, while this work seeks to corroborate the recent diagnosis as a numerical instability problem related to the generation of the potential energy surface. Explicit anharmonic frequencies for c-(CH)C 3 H 2 + are computed using a quartic force field and the CCSD(T)-F12b method with cc-pVDZ-F12, cc-pVTZ-F12, and aug-cc-pVTZ basis sets. The first of these is shown to offer accuracy comparable to that of the latter two with a substantial reduction in computational time. Additionally, c-(CH)C 3 H 2 + is shown to have two fundamental frequencies at the onset of the interstellar unidentified infrared bands, at 5.134 and 6.088 μm or 1947.9 and 1642.6 cm −1 , respectively. This suggests that the results in the present study should assist in the attribution of parts of these aromatic bands, as well as provide data in supportmore »of the laboratory or astronomical detection of c-(CH)C 3 H 2 + .« less
  3. Recently, over 200 molecules have been detected in the interstellar medium (ISM), with about one third being complex organic molecules (COMs), molecules containing six or more atoms. Over the last few decades, astrophysical laboratory experiments have shown that several COMs are formed via interaction of ionizing radiation within ices deposited on interstellar dust particles at 10 K (H 2 O, CH 3 OH, CO, CO 2 , CH 4 , NH 3 ). However, there is still a lack of understanding of the chemical complexity that is available through individual ice constituents. The present research investigates experimentally the synthesis of carbon, hydrogen, and oxygen bearing COMs from interstellar ice analogues containing carbon monoxide (CO) and methane (CH 4 ), ethane (C 2 H 6 ), ethylene (C 2 H 4 ), or acetylene (C 2 H 2 ) exposed to ionizing radiation. Utilizing online and in situ techniques, such as infrared spectroscopy and tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS), specific isomers produced could be characterized. A total of 12 chemically different groups were detected corresponding to C 2 H n O ( n = 2, 4, 6), C 3 H n O ( n = 2, 4, 6, 8),more »C 4 H n O ( n = 4, 6, 8, 10), C 5 H n O ( n = 4, 6, 8, 10), C 6 H n O ( n = 4, 6, 8, 10, 12, 14), C 2 H n O 2 ( n = 2, 4), C 3 H n O 2 ( n = 4, 6, 8), C 4 H n O 2 ( n = 4, 6, 8, 10), C 5 H n O 2 ( n = 6, 8), C 6 H n O 2 ( n = 8, 10, 12), C 4 H n O 3 ( n = 4, 6, 8), and C 5 H n O 3 ( n = 6, 8). More than half of these isomer specifically identified molecules have been identified in the ISM, and the remaining COMs detected here can be utilized to guide future astronomical observations. Of these isomers, three groups – alcohols, aldehydes, and molecules containing two of these functional groups – displayed varying degrees of unsaturation. Also, the detection of 1-propanol, 2-propanol, 1-butanal, and 2-methyl-propanal has significant implications as the propyl and isopropyl moieties (C 3 H 7 ), which have already been detected in the ISM via propyl cyanide and isopropyl cyanide, could be detected in our laboratory studies. General reaction mechanisms for their formation are also proposed, with distinct follow-up studies being imperative to elucidate the complexity of COMs synthesized in these ices.« less

    In this work, by means of quantum chemistry (Density Functional Theory (DFT), PW6B95/def2-TZVPP; DLPNO-CCSD(T)/CBS), HCN polymerization [(HCN)1 − 4] initiated and catalysed by a siloxyl radical (Si-O•) on a model silica surface is analysed. Linear HCN polymers (pHCN) are obtained by a radical initiated mechanism at a SiO• site and are characterized by a -(HC-N)- skeleton due to radical localization on the terminal N atom and radical attack on the C centre. NC heterocycles are formed by cyclization of the linear SiO-(HCN)3 − 4 and are always thermodynamically preferred over their linear counterparts, acting as thermodynamic sinks. Of particular interest to the astrochemistry community is the formation of the N-heterocycle 1,3,5-triazine that can be released into the gas phase at relatively low T (ΔG† = 23.3 kcal/mol). Full hydrogenation of SiO-(HCN•) follows two reaction channels with products: (a) SiO-CH3 + •NH2 or (b) amino-methanol + Si•, though characterized by slow kinetics. Nucleophilic addition of H2O to the electron-rich SiO-(HCN•) shows an unfavourable thermodynamics as well as a high-activation energy. The cleavage of the linear (HCN)1−4 from the SiO• site also shows a high thermodynamic energy penalty (ΔG≥82.0 kcal/mol). As a consequence, the silicate surface will be passivated by a chemically active ‘pHCN brush’ modifying the surface physico-chemical properties. The prospect ofmore »surface-catalysed HCN polymers exhibiting a high degree of chemical reactivity and proposed avenues for the formation of 1,3,5-triazine and amino-methanol opens exciting new chemical pathways to Complex Organic Matter formation in astrochemistry.

    « less
  5. Abstract

    We report the detection of the CO(12–11) line emission toward G09-83808 (or H-ATLAS J090045.4+004125), a strongly-lensed submillimeter galaxy at z = 6.02, with Atacama Large Millimeter/submillimeter Array observations. Combining previously detected [O iii] 88 μm, [N ii] 205 μm, and dust continuum at 0.6 mm and 1.5 mm, we investigate the physical properties of the multi-phase interstellar medium in G09-83808. A source-plane reconstruction reveals that the region of the CO(12–11) emission is compact ($R_\mathrm{{e, CO}}=0.49^{+0.29}_{-0.19}\:\mbox{kpc}$) and roughly coincides with that of the dust continuum. Non-local thermodynamic equilibrium radiative transfer modeling of CO spectral-line energy distribution reveals that most of the CO(12–11) emission comes from a warm (kinetic temperature of Tkin = 320 ± 170 K) and dense [log (nH2/cm−3) = 5.4 ± 0.6] gas, indicating that the warm and dense molecular gas is concentrated in the central 0.5 kpc region. The luminosity ratio in G09-83808 is estimated to be LCO(12-11)/LCO(6-5) = 1.1 ± 0.2. The high ratio is consistent with those in local active galactic nuclei (AGNs) and 6 < z < 7 quasars, the fact of which implies that G09-83808 would be a good target to explore dust-obscured AGNs in the epoch of reionization. In the reconstructed [O iii] 88 μm and [N ii] 205 μm cubes, we also find that a monotonic velocity gradientmore »is extending over the central starburst region by a factor of 2 and that star-forming sub-components exist. High-resolution observations of bright [C ii] 158 μm line emissions will enable us to characterize the kinematics of a possible rotating disk and the nature of the sub-components.

    « less