| Full text | |
| Author(s): |
Vichietti, Rafael Mario
;
Keidel Spada, Rene Felipe
;
Ferreira da Silva, Alberico Borges
;
Correto Machado, Francisco Bolivar
;
Andrade Haiduke, Roberto Luiz
Total Authors: 5
|
| Document type: | Journal article |
| Source: | CHEMISTRYSELECT; v. 2, n. 24, p. 7267-7272, AUG 22 2017. |
| Web of Science Citations: | 2 |
| Abstract | |
The forward and reverse H2O + CO <-> HCOOH reactions were investigated using high-level methodologies in order to provide accurate thermodynamic and kinetic data between 200 and 4000K. Geometries of reactants, transition state (TS), and product were determined with the Coupled Cluster Theory including single and double excitations (CCSD) along with the cc-pVTZ basis set, whereas associated vibrational frequencies, zero-point energies, and thermal corrections were scaled to consider anharmonicity effects. Besides, the description of electronic energies was improved by means of core-valence correlation and iterative triple-excitation contributions together with a complete basis set extrapolation (E-CBS,E-Delta) in order to achieve accurate values of enthalpies, Gibbs energies, and rate constants. Such rate constants were estimated at the high-pressure limit by variational TS treatments combined with different quantum tunneling approaches. Finally, modified Arrhenius' equations were fitted between 700 and 4000K from our most reliable results. (AU) | |
| FAPESP's process: | 17/07707-3 - Excited states and biradicalar nature of poliacenes and periacenes |
| Grantee: | Francisco Bolivar Correto Machado |
| Support Opportunities: | Regular Research Grants |
| FAPESP's process: | 10/18743-1 - Employment of multipoles from the quantum theory of atoms in molecules and kinetic studies in systems found in the interstellar medium |
| Grantee: | Roberto Luiz Andrade Haiduke |
| Support Opportunities: | Regular Research Grants |
| FAPESP's process: | 14/23714-1 - Electronic structure relativistic calculations for evaluation of new prolapse-free basis sets |
| Grantee: | Roberto Luiz Andrade Haiduke |
| Support Opportunities: | Regular Research Grants |