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Insights into the interactions of CO2 with amines: a DFT benchmark study.
| Content Provider | Semantic Scholar |
|---|---|
| Author | Orestes, Ednilsom Ronconi, Célia Machado Carneiro, Jose Walkimar De M. |
| Copyright Year | 2014 |
| Abstract | The interaction between CO2 and 1,2-diaminoethane was computed using pure and hybrid density functionals. The CAM-B3LYP and wB97X-D functionals using a triple-ζ basis set that includes diffuse and polarization functions are the best functionals for calculating the relative energies of the zwitterion intermediate compared to a coupled-cluster with a single, double and non-iterative triple excitation (CCSD(T)) approach extrapolated to a complete basis set limit. With the two functionals and the triple-ζ basis set, the zwitterion is 1.70 kcal mol(-1) less stable than the reactants, and close to 1.63 kcal mol(-1) computed using the CCSD(T) approach. The inclusion of vibrational and thermal corrections and of entropic effects increases the relative energy of the zwitterion to 14.7 kcal mol(-1). Bending of the CO2 geometry increases its acidity due to a 1.09 eV reduction in the LUMO energy. Calculation of the CO2 interaction energy with a set of amines revealed that the interaction energies show a high correlation with their basicities, with the stronger bases stabilizing the zwitterion. For the most basic amine computed (3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine), the Gibbs free energy of the zwitterion is 15.8 kcal mol(-1) lower than the reactants. Therefore, for this highly basic amine, the zwitterion may have a longer lifetime, in contrast to 2-aminoethanol (MEA), where it is only a transient species. |
| Starting Page | 3201 |
| Ending Page | 3217 |
| Page Count | 17 |
| File Format | PDF HTM / HTML |
| Alternate Webpage(s) | http://www.rsc.org/suppdata/cp/c4/c4cp02254h/c4cp02254h1.pdf |
| Alternate Webpage(s) | http://pubs.rsc.org/en/content/getauthorversionpdf/C4CP02254H |
| PubMed reference number | 25014069v1 |
| Alternate Webpage(s) | https://doi.org/10.1039/c4cp02254h |
| DOI | 10.1039/c4cp02254h |
| Journal | Physical chemistry chemical physics : PCCP |
| Volume Number | 16 |
| Issue Number | 32 |
| Language | English |
| Access Restriction | Open |
| Subject Keyword | Amines Base Carbon Dioxide Cysteamine Energy, Physics Ethylenediamine Excitation chorioallantoic membrane ethanolamine free energy kilocalorie |
| Content Type | Text |
| Resource Type | Article |
