| Full text | |
| Author(s): |
Schneider, Felipe S. S.
[1]
;
Setiadi, Jeffry
[2]
;
Felisberti, Maria Isabel
[3]
;
Vazquez, Pedro A. M.
[3]
;
da Conceicao, Thiago Ferreira
[1]
;
Heinzelmann, Germano
[4]
;
Caramori, Giovanni Finoto
[1]
Total Authors: 7
|
| Affiliation: | [1] Univ Fed Santa Catarina, Dept Quim, Campus Univ Trindade, CP 476, BR-88040900 Florianopolis, SC - Brazil
[2] Univ Sydney, Sch Phys, Sydney, NSW 2006 - Australia
[3] Univ Campinas UNICAMP, Inst Chem, POB 6154, BR-13083970 Campinas, SP - Brazil
[4] Univ Fed Santa Catarina, Dept Fis, Campus Univ Trindade, BR-88040900 Florianopolis, SC - Brazil
Total Affiliations: 4
|
| Document type: | Journal article |
| Source: | COMPUTATIONAL AND THEORETICAL CHEMISTRY; v. 1147, p. 13-19, JAN 1 2019. |
| Web of Science Citations: | 0 |
| Abstract | |
Aniline aminolysis reaction of pyromellitic (PMDA) and 1,4,5,8-naphthalenetetracarboxylic (NTDA) dianhydrides is investigated by means of density functional theory (BP86-D3(BJ)/def2-TZVP). The concerted mechanism is shown to be more favorable for both substrates, in comparison to the stepwise one, with the aminolysis of PMDA presenting lower activation energy than the reaction of NTDA. This result is shown to be related to the lower ring tension in NTDA. Solvation also shows significant influence on the kinetics and thermodynamics of these reactions, as determined by two different methods, implicit with the universal solvation model SMD, and explicit with alchemical FEP molecular dynamics simulations. The comparison between SMD and FEP enables us to explore possible inaccuracies on the SMD model, and examine the suitability of the FEP approach as a physics-based method for the calculation of the solvent contribution in different reactions. (AU) | |
| FAPESP's process: | 10/18268-1 - Preparation and processing of nanocomposites of polyimides with carbon nanotubes and graphen |
| Grantee: | Thiago Ferreira da Conceição |
| Support Opportunities: | Scholarships in Brazil - Post-Doctoral |