Volume 532, August 2011
|Number of page(s)||6|
|Section||Interstellar and circumstellar matter|
|Published online||12 July 2011|
Differential adsorption of complex organic molecules isomers at interstellar ice surfaces
UPMC Univ. Paris 06, UMR - CNRS 7616, Laboratoire de Chimie Théorique (LCT), 75005 Paris, France
2 UPMC Univ. Paris 06, UMR - CNRS 7092, Laboratoire de Physique Moléculaire pour l′Atmosphère et l′Astrophysique (LPMAA), 75005 Paris, France
3 Observatoire de Paris et Université de Cergy Pontoise, UMR-CNRS 8112, Laboratoire d’Étude du Rayonnement et de la Matière en Astrophysique/Laboratoire Atomes et Molécules en Astrophysique (LERMA/LAMAp), 95000 Cergy Pontoise, France
Received: 23 November 2010
Accepted: 7 May 2011
Context. Over 20 of the ~150 different species detected in the interstellar and circumstellar media have also been identified in icy environments. For most of the species observed so far in the interstellar medium (ISM), the most abundant isomer of a given generic chemical formula is the most stable one (minimum energy principle – MEP) with few exceptions such as, for example, CH3COOH/HCOOCH3 and CH3CH2OH/CH3OCH3, whose formation is thought to occur on the icy mantles of interstellar grains.
Aims. We investigate whether differences found in the compositions of molecular ices and the surrounding gas phase could originate from differences between the adsorption of one isomer from that of another at the ice surface.
Methods. We performed a coherent and concerted theoretical/experimental study of the adsorption energies of the four molecules mentioned above, i.e. acetic acid (AA)/methyl formate (MF) and ethanol (EtOH)/dimethyl ether (DME) on the surface of water ice at low temperature. The question was first addressed theoretically at LCT using solid state periodic density functional theory (DFT) to represent the organized solid support. The experimental determination of the ice/molecule interaction energies was then carried out independently by two teams at LPMAA and LERMA/LAMAp using temperature programmed desorption (TPD) under an ultra-high vacuum (UHV) between 70 and 160 K.
Results. For each pair of isomers, theory and experiments both agree that the most stable isomer (AA or EtOH) interacts more efficiently with the water ice than the higher energy isomer (MF or DME). This differential adsorption can be clearly seen in the different desorption temperatures of the isomers. It is not related to their intrinsic stability but instead to both AA and EtOH producing more and stronger hydrogen bonds with the ice surface.
Conclusions. We show that hydrogen bonding may play an important role in the release of organic species from grains and propose that, depending on the environment, differential adsorption should not be rejected as a possible way of interpreting MEP exceptions.
Key words: astrochemistry / ISM: abundances / ISM: molecules
© ESO, 2011
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