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Is the Reaction Between Formic Acid and Protonated Aminomethanol a Possible Source of Glycine Precursors in the Interstellar Medium?

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Is the Reaction Between Formic Acid and Protonated Aminomethanol a Possible Source of Glycine Precursors in the Interstellar Medium? A&A 579, A125 (2015) Astronomy DOI: 10.1051/0004-6361/201526548 & c ESO 2015 Astrophysics Is the reaction between formic acid and protonated aminomethanol a possible source of glycine precursors in the interstellar medium? Pilar Redondo, Antonio Largo, and Carmen Barrientos Computational Chemistry Group, Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011 Valladolid, Spain e-mail: [predondo;alargo;cbb]@qf.uva.es Received 18 May 2015 / Accepted 28 May 2015 ABSTRACT Context. One of the most interesting questions in interstellar chemistry concerns whether we can detect the basic building blocks of proteins in astronomical sources. In ascertaining whether amino acids could be possible interstellar molecules, a crucial point is how they could be synthesized in the interstellar medium. Aims. We do a theoretical study of the ion-molecule reaction involving protonated aminomethanol and formic acid to establish its viability in space. This ion-molecule reaction has been proposed by other authors as a possible way to produce glycine in the interstellar medium. Methods. The relevant stationary points on the potential energy surface of the reaction between protonated aminomethanol and formic acid have been theoretically studied by using ab initio methods. The second-order Moller-Plesset level was employed, in conjunction with the correlation-consistent polarized valence triple-zeta (cc-pVTZ) basis set. In addition, the electronic energies were refined by means of single-point calculations at the CCSD(T) level (coupled cluster single and double excitation model augmented with a non-iterative treatment of triple excitations) on the MP2/cc-pVTZ geometries with the aug-cc-pVTZ basis set. Results. Formation of protonated glycine is an exothermic process; however, the process presents a net activation barrier that makes this reaction unfeasible under interstellar conditions. Conclusions. The reaction of protonated aminomethanol with formic acid does not seem to be a plausible source of interstellar glycine. This particular case is a clear example that a detailed study of the potential energy surface is needed to establish the relevance of a process in the interstellar medium. Key words. astrobiology – astrochemistry – molecular processes – ISM: kinematics and dynamics – ISM: molecules – ISM: general 1. Introduction (gas-phase, grain-surface, and bulk-ice) chemical model of hot cores (Garrod 2013) predicts that detection of glycine with in- Around 180 molecular species have been detected so far in the struments like ALMA that have greater sensitivity and spatial interstellar medium, and the list is increasing every year. These resolution could be plausible. detections suggest a much richer chemistry than previously ex- To ascertain whether amino acids could be possible interstel- pected in the interstellar medium. One of the most complex ques- lar molecules, a crucial point is how they could be synthesized in tions in interstellar chemistry concerns the possible existence of the interstellar medium. In view of the experimental results men- bio-molecules. Undoubtedly, finding bio-molecules in the inter- tioned earlier, a possible way of obtaining amino acids is through stellar medium would have a deep impact on our vision of the reactions on the surface of interstellar dust particles. Different origin of life. It is not surprising that so much effort has been theoretical studies have been carried out on possible synthetic devoted to finding amino acids, the basic building blocks of pro- pathways taking place on the surface of interstellar grains lead- teins, in astronomical sources. In particular, the simplest amino ing to precursors of glycine (Woon 2001, 2002a,b; Rimola et al. acid, glycine, has been searched for recursively, although with 2010, 2012). In most of these studies, the reactions that were no success so far (Hollis et al. 1980; Snyder et al. 1983, 2005; considered involved radical species. Ceccarelli et al. 2000; Hollis et al. 2003a,b; Kuan et al. 2003; In addition, amino acids could also be formed through gas Jones et al. 2007; Cunningham et al. 2007). phase reactions. Several proposals of different neutral-neutral re- Nevertheless, there is observational evidence of amino acids actions have been made (Hoyle 1976; Maeda & Ohno 2004a,b, in extraterrestrial objects, such as meteorites (Cronin & Pizarello 2006; Basiuk & Kobayashi 2004; Andreazza et al. 2006). In 1997; Ehrenfreund et al. 2001; Glavin et al. 2010; Burton et al. some cases theoretical studies have been carried out (Basiuk & 2013)orcomets(Elsila et al. 2009). Furthermore, different ex- Bogillo 2000; Basiuk 2001) that conclude that these processes periments have shown the formation of amino acids after UV ir- are not feasible under interstellar conditions. Ion-molecule reac- radiation of interstellar ice analogues (Bernstein et al. 2002; tions are more promising, since in many cases they are more Muñoz-Caro et al. 2002; Holtom et al. 2005; Elsila et al. 2007). likely to proceed without involving energy barriers. Different Therefore, even though no conclusive detection of an amino ion-molecule processes have been invoked as possible sources acid in the interstellar medium has been reported, it is conceiv- of glycine precursors. Experimental (Jackson et al. 2005a,b) able that they could be present in space. A recent three-phase and theoretical (Largo et al. 2004, 2008, 2010) studies of the Article published by EDP Sciences A125, page 1 of 6 A&A 579, A125 (2015) reactions of ammonia cations with formic and acetic acids and with the aug-cc-pVTZ basis set. For these geometries single- of different neutrals with amines have been carried out. Some point calculations at the CCSD(T) were performed with the of these reactions involve significant barriers, whereas other aug-cc-pVQZ basis set (correlation-consistent polarized va- barrier-free processes leading to precursors of glycine are less lence quadruple-zeta including diffuse functions Dunning 1989; favorable than other competing channels. Kendall et al. 1992). All calculations reported in this work were Precursors of glycine and alanine were obtained in ex- carried out with the Gaussian-09 program package (Frisch at al. periments involving ion-molecule reactions of hydroxylamine 2010). derivatives and carboxylic acids (Blagojevic et al. 2003; Snow et al. 2007). However, a recent theoretical study (Barrientos 3. Results and discussion et al. 2012) has concluded that production of glycine from the reaction of either cationic or protonated hydroxylamine should Formic acid (HCOOH) is a molecule present in the interstel- be fairly inefficient under interstellar conditions, a result which lar medium (Zuckerman et al. 1971; Winnewisser & Churchwell agrees with a recently model developed by Garrod (2013). 1975) that can evolve to more complex systems. Despite, Therefore, until now there seems to be no successful proposal aminomethanol (NH2CH2OH) is considered to be a key prebi- for a gas-phase reaction that could lead to precursors of inter- otic interstellar molecule, it remains undetected in space, in part stellar glycine. because of the difficulties synthethizing it in terrestrial laborato- In the present work we perform a theoretical study of ries, which makes it difficult to obtain a complete spectroscopic the viability of the ion-molecule reaction involving protonated characterization. It has been predicted that aminomethanol is aminomethanol and formic acid in space. This reaction has been formed in interstellar ices through a radical-radical reaction proposed by other authors as one route toward producing glycine between NH2 and CH2OH, which are created in the photol- in the interstellar medium (Charnley 1999; Charnley et al. 2001; ysis of ammonia and methanol, respectively (Garrod et al. Kuan et al. 2003). However, to the best of our knowledge, this 2008). The experimental work of Bossa et al. (2009)showsthat reaction has not been previously studied theoretically or experi- aminomethanol is formed from the thermal reaction of NH3 and mentally. The paper is structured as follows. In the second sec- H2CO in interstellar-ice analogues at low temperatures. They tion, we introduce the computational methods used in our study. conclude that NH2CH2OH should be detectable in the gas phase Section 3 first presents the protonation of aminomethanol under in warm environments where the icy material is desorbed. From interstellar conditions, and then the potential energy surface of a theoretical point of view, inserting O(1D) into the C-H bond the reaction of protonated aminomethanol with formic acid is of methyl amine gives aminomethanol as the most energeti- analyzed. In the last section, we summarize the main findings of cally favored pathway (Hays & Widicus Weaver 2013). A sim- our study. ulation of the spectrum of aminomethanol based on its opti- mized geometry has also been reported. Feldmann et al. (2005) analyzed the stability of aminomethanol with respect to the 2. Computational methods loss of one water molecule and its conversion to methanimine. The calculated barrier height (about 55 kcal/mol) indicates that The characterization of stationary points on the potential en- aminomethanol is stable in relation to this process. Finally, ergy surface for the reaction of aminomethanol with formic the water-catalyzed reaction of formaldehyde and ammonia for acid employed similar theoretical methods to our previous work generating NH2CH2OH has been also studied (Courmier et al. on related systems
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