skip to main content

Explore Research Products in the NSF-PAR

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 → 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.  more » « less
Award ID(s):
1757220
NSF-PAR ID:
10335940
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Astronomy & Astrophysics
Volume:
656
ISSN:
0004-6361
Page Range / eLocation ID:
A148
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ( , The Astrophysical Journal)
    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.

     
    more » « less
  2. ; ; ( , Monthly Notices of the Royal Astronomical Society)
    ABSTRACT

    Nearly two decades since the detection of cyclopropenone (c-C3H2O) in the interstellar medium (ISM), the understanding of how this molecule comes to be remains incomplete. Many hypotheses place the ubiquitous hydrocarbon c-C3H2 at the centre of such discussions. However, insights into c-C3H2 chemistry are further complicated by the recent detection of ethynyl cyclopropenylidene (c-C3HC2H) and the observation of a radio line possibly belonging to methylenecyclopropene (c-C3H2CH2). In a necessary reconciliation of past and current work on the chemical capabilities of c-C3H2 in interstellar environments, the formation pathways of several functionalized cyclopropenes from c-C3H2 and a hydrogenated radical are explored. Chemically accurate CCSD(T)-F12/cc-pVTZ-F12 calculations are used to evaluate the energies of reaction and generate structures along the reaction pathway for formation products deemed chemically plausible. Potential energy scans are used to include or rule out certain paths to product formation based on conformation to the necessary requirements of cold interstellar chemistry. Four functionalized cyclopropenes in addition to c-C3H2O have net exothermic reactions when forming from c-C3H2 (c-C3H2CC, c-C3H2S, c-C3H2NH, and c-C3H2CH2). The former three are found to have reaction profiles favourable for formation in the cold ISM, while c-C3H2CH2 can only form by passage through an association barrier that must be mitigated by an energy source of some kind. c-C3H2S and c-C3H2NH are the best candidates for new spectroscopic searches. A complete detection of c-C3H2CH2 is necessary to fully understand cyclopropenylidene chemistry in the ISM.

     
    more » « less
  3. ; ; ; ( , Physical Chemistry Chemical Physics)
    null (Ed.)
    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 support of the laboratory or astronomical detection of c-(CH)C 3 H 2 + . 
    more » « less
  4. ; ; ; ; ; ; ; ; ; ; et al ( , Astronomy & Astrophysics)

    Water vapor (H2O) is one of the brightest molecular emitters after carbon monoxide (CO) in galaxies with high infrared (IR) luminosity, allowing us to investigate the warm and dense phase of the interstellar medium (ISM) where star formation occurs. However, due to the complexity of its radiative spectrum, H2O is not frequently exploited as an ISM tracer in distant galaxies. Therefore, H2O studies of the warm and dense gas at high-zremain largely unexplored. In this work, we present observations conducted with the Northern Extended Millimeter Array (NOEMA) toward threez > 6 IR-bright quasarsJ2310+1855,J1148+5251, andJ0439+1634targeted in their multiple para- and ortho-H2O transitions (312 − 303, 111 − 000, 220 − 211, and 422 − 413), as well as their far-IR (FIR) dust continuum. By combining our data with previous measurements from the literature, we estimated the dust masses and temperatures, continuum optical depths, IR luminosities, and star formation rates (SFR) from the FIR continuum. We modeled the H2O lines using the MOLPOP-CEP radiative transfer code, finding that water vapor lines in our quasar host galaxies are primarily excited in the warm, dense (with a gas kinetic temperature and density ofTkin = 50 K,nH2 ∼ 104.5 − 105 cm−3) molecular medium with a water vapor column density ofNH2O ∼ 2 × 1017 − 3 × 1018 cm−3. High-JH2O lines are mainly radiatively pumped by the intense optically-thin far-IR radiation field associated with a warm dust component at temperatures ofTdust ∼ 80 − 190 K that account for < 5 − 10% of the total dust mass. In the case of J2310+1855, our analysis points to a relatively high value of the continuum optical depth at 100 μm (τ100 ∼ 1). Our results are in agreement with expectations based on the H2O spectral line energy distribution of local and high-zultra-luminous IR galaxies and active galactic nuclei (AGN). The analysis of the Boltzmann diagrams highlights the interplay between collisions and IR pumping in populating the high H2O energy levels and it allows us to directly compare the excitation conditions in the targeted quasar host galaxies. In addition, the observations enable us to sample the high-luminosity part of the H2O–total-IR (TIR) luminosity relations (LH2O − LTIR). Overall, our results point to supralinear trends that suggest H2O–TIR relations are likely driven by IR pumping, rather than the mere co-spatiality between the FIR continuum- and line-emitting regions. The observedLH2O/LTIRratios in ourz > 6 quasars do not show any strong deviations with respect to those measured in star-forming galaxies and AGN at lower redshifts. This supports the notion that H2O can be likely used to trace the star formation activity buried deep within the dense molecular clouds.

     
    more » « less
  5. ; ; ; ; ; ; ; ; ( , Astronomy & Astrophysics)
    Context. Atomic gas in the diffuse interstellar medium (ISM) is organized in filamentary structures. These structures usually host cold and dense molecular clumps. The Galactic magnetic field is considered to play an important role in the formation of these clumps. Aims. Our goal is to explore the role of the magnetic field in the H I -H 2 transition process. Methods. We targeted a diffuse ISM filamentary cloud toward the Ursa Major cirrus where gas transitions from atomic to molecular. We probed the magnetic field properties of the cloud with optical polarization observations. We performed multiwavelength spectroscopic observations of different species in order to probe the gas phase properties of the cloud. We observed the CO ( J = 1−0) and ( J = 2−1) lines in order to probe the molecular content of the cloud. We also obtained observations of the [C ii ] 157.6 µ m emission line in order to trace the CO-dark H 2 gas and estimate the mean volume density of the cloud. Results. We identified two distinct subregions within the cloud. One of the regions is mostly atomic, while the other is dominated by molecular gas, although most of it is CO-dark. The estimated plane-of-the-sky magnetic field strength between the two regions remains constant within uncertainties and lies in the range 13–30 µG. The total magnetic field strength does not scale with density. This implies that gas is compressed along the field lines. We also found that turbulence is trans-Alfvénic, with M A ≈ 1. In the molecular region, we detected an asymmetric CO clump whose minor axis is closer, with a 24° deviation, to the mean magnetic field orientation than the angle of its major axis. The H i velocity gradients are in general perpendicular to the mean magnetic field orientation except for the region close to the CO clump, where they tend to become parallel. This phenomenon is likely related to gas undergoing gravitational infall. The magnetic field morphology of the target cloud is parallel to the H i column density structure of the cloud in the atomic region, while it tends to become perpendicular to the H i structure in the molecular region. On the other hand, the magnetic field morphology seems to form a smaller offset angle with the total column density shape (including both atomic and molecular gas) of this transition cloud. Conclusions. In the target cloud where the H i –H 2 transition takes place, turbulence is trans-Alfvénic, and hence the magnetic field plays an important role in the cloud dynamics. Atomic gas probably accumulates preferentially along the magnetic field lines and creates overdensities where molecular gas can form. The magnetic field morphology is probed better by the total column density shape of the cloud, and not its H i column density shape. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email