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Title: Revisiting the reactivity between HCO and CH3 on interstellar grain surfaces

Abstract

The formation of interstellar complex organic molecules is currently thought to be dominated by the barrierless coupling between radicals on the interstellar icy grain surfaces. Previous standard density functional theory (DFT) results on the reactivity between CH3 and HCO on amorphous water surfaces showed that the formation of CH4 + CO by H transfer from HCO to CH3 assisted by water molecules of the ice was the dominant channel. In contrast, the adopted description of the electronic structure of the biradical (i.e. CH3/HCO) system was inadequate [without the broken-symmetry (BS) approach]. In this work, we revisit the original results by means of BS-DFT both in gas phase and with one water molecule simulating the role of the ice. Results indicate that the adoption of BS-DFT is mandatory to describe properly biradical systems. In the presence of the single water molecule, the water-assisted H transfer exhibits a high energy barrier. In contrast, CH3CHO formation is found to be barrierless. Yet, direct H transfer from HCO to CH3 to give CO and CH4 presents a very low energy barrier, hence being a potential competitive channel to the radical coupling and indicating, moreover, that the physical insights of the original work remain valid.

Authors:
 [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6];  [7]; ORCiD logo [8]; ORCiD logo [9]; ORCiD logo [3]
  1. Univ. of Grenoble (France); Univ. Autonoma de Barcelona (Spain)
  2. Univ. of Stuttgart (Germany)
  3. Univ. of Stuttgart (Germany)
  4. Univ. Autonoma de Barcelona (Spain)
  5. Univ. of Grenoble (France)
  6. Univ. of Grenoble (France); Univ. degli Studi di Perugia (Italy); Istituto Nazionale di Astrofisica (INAF), Firenze (Italy). Osservatorio Astrofisico di Arcetri
  7. Univ. of Stuttgart (Germany); Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
  8. Univ. of Turin, Torino (Italy). Centre for Nanostructured Interfaces and Surfaces (NIS)
  9. Univ. of Stuttgart (Germany); Leiden Univ. (Netherlands)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1616759
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Monthly Notices of the Royal Astronomical Society
Additional Journal Information:
Journal Volume: 493; Journal Issue: 2; Journal ID: ISSN 0035-8711
Publisher:
Royal Astronomical Society
Country of Publication:
United States
Language:
English
Subject:
79 ASTRONOMY AND ASTROPHYSICS; astrochemistry; molecular processes; ISM: clouds; ISM: molecules

Citation Formats

Enrique-Romero, J., Álvarez-Barcia, S., Kolb, F. J., Rimola, A., Ceccarelli, C., Balucani, N., Meisner, J., Ugliengo, P., Lamberts, T., and Kästner, J. Revisiting the reactivity between HCO and CH3 on interstellar grain surfaces. United States: N. p., 2020. Web. https://doi.org/10.1093/mnras/staa484.
Enrique-Romero, J., Álvarez-Barcia, S., Kolb, F. J., Rimola, A., Ceccarelli, C., Balucani, N., Meisner, J., Ugliengo, P., Lamberts, T., & Kästner, J. Revisiting the reactivity between HCO and CH3 on interstellar grain surfaces. United States. https://doi.org/10.1093/mnras/staa484
Enrique-Romero, J., Álvarez-Barcia, S., Kolb, F. J., Rimola, A., Ceccarelli, C., Balucani, N., Meisner, J., Ugliengo, P., Lamberts, T., and Kästner, J. Thu . "Revisiting the reactivity between HCO and CH3 on interstellar grain surfaces". United States. https://doi.org/10.1093/mnras/staa484. https://www.osti.gov/servlets/purl/1616759.
@article{osti_1616759,
title = {Revisiting the reactivity between HCO and CH3 on interstellar grain surfaces},
author = {Enrique-Romero, J. and Álvarez-Barcia, S. and Kolb, F. J. and Rimola, A. and Ceccarelli, C. and Balucani, N. and Meisner, J. and Ugliengo, P. and Lamberts, T. and Kästner, J.},
abstractNote = {The formation of interstellar complex organic molecules is currently thought to be dominated by the barrierless coupling between radicals on the interstellar icy grain surfaces. Previous standard density functional theory (DFT) results on the reactivity between CH3 and HCO on amorphous water surfaces showed that the formation of CH4 + CO by H transfer from HCO to CH3 assisted by water molecules of the ice was the dominant channel. In contrast, the adopted description of the electronic structure of the biradical (i.e. CH3/HCO) system was inadequate [without the broken-symmetry (BS) approach]. In this work, we revisit the original results by means of BS-DFT both in gas phase and with one water molecule simulating the role of the ice. Results indicate that the adoption of BS-DFT is mandatory to describe properly biradical systems. In the presence of the single water molecule, the water-assisted H transfer exhibits a high energy barrier. In contrast, CH3CHO formation is found to be barrierless. Yet, direct H transfer from HCO to CH3 to give CO and CH4 presents a very low energy barrier, hence being a potential competitive channel to the radical coupling and indicating, moreover, that the physical insights of the original work remain valid.},
doi = {10.1093/mnras/staa484},
journal = {Monthly Notices of the Royal Astronomical Society},
number = 2,
volume = 493,
place = {United States},
year = {2020},
month = {2}
}

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