Literature DB >> 23965675

Accelerated chemistry in the reaction between the hydroxyl radical and methanol at interstellar temperatures facilitated by tunnelling.

Robin J Shannon1, Mark A Blitz, Andrew Goddard, Dwayne E Heard.   

Abstract

Understanding the abundances of molecules in dense interstellar clouds requires knowledge of the rates of gas-phase reactions between uncharged species. However, because of the low temperatures within these clouds, reactions with an activation barrier were considered too slow to play an important role. Here we show that, despite the presence of a barrier, the rate coefficient for the reaction between the hydroxyl radical (OH) and methanol--one of the most abundant organic molecules in space--is almost two orders of magnitude larger at 63 K than previously measured at ∼200 K. We also observe the formation of the methoxy radical product, which was recently detected in space. These results are interpreted by the formation of a hydrogen-bonded complex that is sufficiently long-lived to undergo quantum-mechanical tunnelling to form products. We postulate that this tunnelling mechanism for the oxidation of organic molecules by OH is widespread in low-temperature interstellar environments.

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Year:  2013        PMID: 23965675     DOI: 10.1038/nchem.1692

Source DB:  PubMed          Journal:  Nat Chem        ISSN: 1755-4330            Impact factor:   24.427


  9 in total

1.  Chemistry of star-forming regions.

Authors:  Eric Herbst
Journal:  J Phys Chem A       Date:  2005-05-12       Impact factor: 2.781

Review 2.  Chemical evolution of star-forming regions.

Authors:  E F van Dishoeck; G A Blake
Journal:  Annu Rev Astron Astrophys       Date:  1998       Impact factor: 30.065

3.  Understanding reactivity at very low temperatures: the reactions of oxygen atoms with alkenes.

Authors:  Hassan Sabbah; Ludovic Biennier; Ian R Sims; Yuri Georgievskii; Stephen J Klippenstein; Ian W M Smith
Journal:  Science       Date:  2007-07-06       Impact factor: 47.728

4.  MESMER: an open-source master equation solver for multi-energy well reactions.

Authors:  David R Glowacki; Chi-Hsiu Liang; Christopher Morley; Michael J Pilling; Struan H Robertson
Journal:  J Phys Chem A       Date:  2012-09-12       Impact factor: 2.781

5.  The temperature-dependence of rapid low temperature reactions: experiment, understanding and prediction.

Authors:  Ian W M Smith; Amy M Sage; Neil M Donahue; Eric Herbst; Donghui Quan
Journal:  Faraday Discuss       Date:  2006       Impact factor: 4.008

6.  Methylhydroxycarbene: tunneling control of a chemical reaction.

Authors:  Peter R Schreiner; Hans Peter Reisenauer; David Ley; Dennis Gerbig; Chia-Hua Wu; Wesley D Allen
Journal:  Science       Date:  2011-06-10       Impact factor: 47.728

7.  Observation of a large negative temperature dependence for rate coefficients of reactions of OH with oxygenated volatile organic compounds studied at 86-112 K.

Authors:  Robin J Shannon; Sally Taylor; Andrew Goddard; Mark A Blitz; Dwayne E Heard
Journal:  Phys Chem Chem Phys       Date:  2010-09-22       Impact factor: 3.676

8.  Kinetics of the reactions of HO with methanol (210-351 K) and with ethanol (216-368 K).

Authors:  T J Dillon; D Hölscher; V Sivakumaran; A Horowitz; J N Crowley
Journal:  Phys Chem Chem Phys       Date:  2005-01-21       Impact factor: 3.676

9.  Pulsed Laval nozzle study of the kinetics of OH with unsaturated hydrocarbons at very low temperatures.

Authors:  Sally E Taylor; Andrew Goddard; Mark A Blitz; Patricia A Cleary; Dwayne E Heard
Journal:  Phys Chem Chem Phys       Date:  2007-11-07       Impact factor: 3.676

  9 in total
  21 in total

1.  Low-temperature reactions: Tunnelling in space.

Authors:  Ian R Sims
Journal:  Nat Chem       Date:  2013-09       Impact factor: 24.427

2.  Kinetics of low-temperature transitions and a reaction rate theory from non-equilibrium distributions.

Authors:  Vincenzo Aquilanti; Nayara Dantas Coutinho; Valter Henrique Carvalho-Silva
Journal:  Philos Trans A Math Phys Eng Sci       Date:  2017-04-28       Impact factor: 4.226

3.  Hemiaminal route for the formation of interstellar glycine: a computational study.

Authors:  Zanele P Nhlabatsi; Priya Bhasi; Sanyasi Sitha
Journal:  J Mol Model       Date:  2019-11-09       Impact factor: 1.810

4.  Sub-Doppler infrared spectroscopy of CH2OH radical in a slit supersonic jet: Vibration-rotation-tunneling dynamics in the symmetric CH stretch manifold.

Authors:  Michael D Schuder; Fang Wang; Chih-Hsuan Chang; David J Nesbitt
Journal:  J Chem Phys       Date:  2017-05-21       Impact factor: 3.488

5.  High-resolution cavity ring-down spectroscopy of the ν1 + ν6 combination band of methanol at 2.0 μm.

Authors:  Hongming Yi; Adam J Fleisher
Journal:  J Chem Phys       Date:  2019-12-21       Impact factor: 3.488

6.  Quantum Roaming in the Complex-Forming Mechanism of the Reactions of OH with Formaldehyde and Methanol at Low Temperature and Zero Pressure: A Ring Polymer Molecular Dynamics Approach.

Authors:  Pablo Del Mazo-Sevillano; Alfredo Aguado; Elena Jiménez; Yury V Suleimanov; Octavio Roncero
Journal:  J Phys Chem Lett       Date:  2019-04-04       Impact factor: 6.475

7.  Gas-phase reactivity of CH3OH toward OH at interstellar temperatures (11.7-177.5 K): experimental and theoretical study.

Authors:  Antonio J Ocaña; Sergio Blázquez; Alexey Potapov; Bernabé Ballesteros; André Canosa; María Antiñolo; Luc Vereecken; José Albaladejo; Elena Jiménez
Journal:  Phys Chem Chem Phys       Date:  2019-03-27       Impact factor: 3.676

8.  Zero- and high-pressure mechanisms in the complex forming reactions of OH with methanol and formaldehyde at low temperatures.

Authors:  Fedor Naumkin; Pablo Del Mazo-Sevillano; Alfredo Aguado; Yury V Suleimanov; Octavio Roncero
Journal:  ACS Earth Space Chem       Date:  2019-05-14       Impact factor: 3.475

9.  Gas phase kinetics of the OH + CH3CH2OH reaction at temperatures of the interstellar medium (T = 21-107 K).

Authors:  A J Ocaña; S Blázquez; B Ballesteros; A Canosa; M Antiñolo; J Albaladejo; E Jiménez
Journal:  Phys Chem Chem Phys       Date:  2018-02-21       Impact factor: 3.676

10.  Low temperature reaction dynamics for CH3OH + OH collisions on a new full dimensional potential energy surface.

Authors:  Octavio Roncero; Alexandre Zanchet; Alfredo Aguado
Journal:  Phys Chem Chem Phys       Date:  2018-10-17       Impact factor: 3.676

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