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J Phys Chem A. 2008 Jun 12;112(23):5113-20. doi: 10.1021/jp800723c. Epub 2008 May 21.

Formation of neutral methylcarbamic acid (CH3NHCOOH) and methylammonium methylcarbamate [CH3NH3+][CH3NHCO2-] at low temperature.

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  • 1Physique des Interactions Ioniques et Moléculaires, UMR 6633, Université de Provence et CNRS,Centre de St Jérôme, case 252, 13397 Marseille Cedex 20, France.

Abstract

We study low temperature reactivity of methylamine (CH3NH2) and carbon dioxide (CO2) mixed within different ratios, using FTIR spectroscopy and mass spectrometry. We report experimental evidence that the methylammonium methylcarbamate [CH3NH3(+)][C3NHCO2(-)] and methylcarbamic acid (CH3NHCOOH) are formed when the initial mixture CH3NH2:CO2 is warmed up to temperatures above 40 K. An excess of CH3NH2 favors the carbamate formation while an excess of CO2 leads to a mixture of both methylammonium methylcarbamate and methylcarbamic acid. Quantum calculations show that methylcarbamic acid molecules are associated into centrosymmetric dimers. Above 230 K, the carbamate breaks down into CH3NH2 and CH3NHCOOH, then this latter dissociates into CH3NH2 and CO2. After 260 K, it remains on the substrate a solid residue made of a well-organized structure coming from the association between the remaining methylcarbamic acid dimers. This study shows that amines can react at low temperature in interstellar ices rich in carbon dioxide which are a privileged place of complex molecules formation, before being later released into "hot core" regions.

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