Understanding the azeotropic diethyl carbonate-water mixture by structural and energetic characterization of DEC(H2O) n heteroclusters
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| 024 | 7 | 0 | |a 10.1007/s00894-015-2593-5 |2 doi |
| 035 | |a (NATIONALLICENCE)springer-10.1007/s00894-015-2593-5 | ||
| 245 | 0 | 0 | |a Understanding the azeotropic diethyl carbonate-water mixture by structural and energetic characterization of DEC(H2O) n heteroclusters |h [Elektronische Daten] |c [Juan Ripoll, Sol Mejía, Matthew Mills, Aída Villa] |
| 520 | 3 | |a 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 | |
| 540 | |a Springer-Verlag Berlin Heidelberg, 2015 | ||
| 690 | 7 | |a Oxygenated fuel-water azeotrope |2 nationallicence | |
| 690 | 7 | |a Non-covalent interaction |2 nationallicence | |
| 690 | 7 | |a Stochastic exploration |2 nationallicence | |
| 690 | 7 | |a Electron density topology |2 nationallicence | |
| 690 | 7 | |a Cooperative effect |2 nationallicence | |
| 700 | 1 | |a Ripoll |D Juan |u Environmental Catalysis Research Group, Chemical Engineering Department, Engineering Faculty, Universidad de Antioquia, Calle 70 No. 52-21, Medellin, Colombia |4 aut | |
| 700 | 1 | |a Mejía |D Sol |u 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 |4 aut | |
| 700 | 1 | |a Mills |D Matthew |u Deconstruction Division, Joint BioEnergy Institute, Emeryville, CA, USA |4 aut | |
| 700 | 1 | |a Villa |D Aída |u Environmental Catalysis Research Group, Chemical Engineering Department, Engineering Faculty, Universidad de Antioquia, Calle 70 No. 52-21, Medellin, Colombia |4 aut | |
| 773 | 0 | |t Journal of Molecular Modeling |d Springer Berlin Heidelberg |g 21/4(2015-04-01), 1-13 |x 1610-2940 |q 21:4<1 |1 2015 |2 21 |o 894 | |
| 856 | 4 | 0 | |u https://doi.org/10.1007/s00894-015-2593-5 |q text/html |z Onlinezugriff via DOI |
| 898 | |a BK010053 |b XK010053 |c XK010000 | ||
| 900 | 7 | |a Metadata rights reserved |b Springer special CC-BY-NC licence |2 nationallicence | |
| 908 | |D 1 |a research-article |2 jats | ||
| 949 | |B NATIONALLICENCE |F NATIONALLICENCE |b NL-springer | ||
| 950 | |B NATIONALLICENCE |P 856 |E 40 |u https://doi.org/10.1007/s00894-015-2593-5 |q text/html |z Onlinezugriff via DOI | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Ripoll |D Juan |u Environmental Catalysis Research Group, Chemical Engineering Department, Engineering Faculty, Universidad de Antioquia, Calle 70 No. 52-21, Medellin, Colombia |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Mejía |D Sol |u 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 |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Mills |D Matthew |u Deconstruction Division, Joint BioEnergy Institute, Emeryville, CA, USA |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Villa |D Aída |u Environmental Catalysis Research Group, Chemical Engineering Department, Engineering Faculty, Universidad de Antioquia, Calle 70 No. 52-21, Medellin, Colombia |4 aut | ||
| 950 | |B NATIONALLICENCE |P 773 |E 0- |t Journal of Molecular Modeling |d Springer Berlin Heidelberg |g 21/4(2015-04-01), 1-13 |x 1610-2940 |q 21:4<1 |1 2015 |2 21 |o 894 | ||