caa a22 4500 605512655 CHVBK 20210128100656.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00894-015-2593-5 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2593-5 Understanding the azeotropic diethyl carbonate-water mixture by structural and energetic characterization of DEC(H2O) n heteroclusters [Elektronische Daten] [Juan Ripoll, Sol Mejía, Matthew Mills, Aída Villa] Diethyl carbonate (DEC) is an oxygenated fuel additive. During its synthesis through a promising green process, a DEC-water azeotrope is formed, which decreases DEC production efficiency in the gas phase. Molecular information about this system is scarce but could be of benefit in understanding (and potentially improving) the synthetic process. Therefore, we report a detailed computational study of the conformers of DEC, and their microsolvation with up to four water molecules, with the goal of understanding the observed 1:3 DEC:H2O molar ratio. The most stable DEC conformers (with mutual energy differences < 1.5kcalmol−1) contribute to the energetic and structural properties of the complexes. An exhaustive stochastic exploration of each potential energy surface of DEC-(H2O) n , (where n = 1, 2, 3, 4) heteroclusters discovered 3, 8, 7, and 4 heterodimers, heterotrimers, heterotetramers, and heteropentamers, respectively, at the MP2/6-311++G(d,p) level of theory. DEC conformers and energies of the most stable structures at each heterocluster size were refined using CCSD(T)/6-311++G(d,p). Energy decomposition, electron density topology, and cooperative effects analyses were carried out to determine the relationship between the geometrical features of the heteroclusters and the non-covalent interaction types responsible for their stabilization. Our findings show that electrostatic and exchange energies are responsible for heterocluster stabilization, and also suggest a mutual weakening among hydrogen bonds when more than three water molecules are present. All described results are complementary and suggest a structural and energetic explanation at the molecular level for the experimental molar ratio of 1:3 (DEC:H2O) for the DEC-water azeotrope. Graphical Abstract Molecular understanding of the DEC-Water system: energy and structural data Springer-Verlag Berlin Heidelberg, 2015 Oxygenated fuel-water azeotrope nationallicence Non-covalent interaction nationallicence Stochastic exploration nationallicence Electron density topology nationallicence Cooperative effect nationallicence Ripoll Juan Environmental Catalysis Research Group, Chemical Engineering Department, Engineering Faculty, Universidad de Antioquia, Calle 70 No. 52-21, Medellin, Colombia aut Mejía Sol Grupo de Investigación Fitoquímica Universidad Javeriana (GIFUJ), Departamento de Química, Facultad de Ciencias, Pontificia Universidad Javeriana, Carrera 7 No. 40-62, Bogotá, D. C., Colombia aut Mills Matthew Deconstruction Division, Joint BioEnergy Institute, Emeryville, CA, USA aut Villa Aída Environmental Catalysis Research Group, Chemical Engineering Department, Engineering Faculty, Universidad de Antioquia, Calle 70 No. 52-21, Medellin, Colombia aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-13 1610-2940 21:4<1 2015 21 894 https://doi.org/10.1007/s00894-015-2593-5 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2593-5 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Ripoll Juan Environmental Catalysis Research Group, Chemical Engineering Department, Engineering Faculty, Universidad de Antioquia, Calle 70 No. 52-21, Medellin, Colombia aut NATIONALLICENCE 700 1- Mejía Sol Grupo de Investigación Fitoquímica Universidad Javeriana (GIFUJ), Departamento de Química, Facultad de Ciencias, Pontificia Universidad Javeriana, Carrera 7 No. 40-62, Bogotá, D. C., Colombia aut NATIONALLICENCE 700 1- Mills Matthew Deconstruction Division, Joint BioEnergy Institute, Emeryville, CA, USA aut NATIONALLICENCE 700 1- Villa Aída Environmental Catalysis Research Group, Chemical Engineering Department, Engineering Faculty, Universidad de Antioquia, Calle 70 No. 52-21, Medellin, Colombia aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-13 1610-2940 21:4<1 2015 21 894