RT Journal Article
T1 Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry
A1 García Martínez, Antonio
A1 Siehl, Hans-Ulrich
A1 Moya Cerero, Santiago De La
A1 Gómez Calzada, Pedro Carlos
AB An expeditious procedure for the challenging computation of the free energy barriers (DGa) for the solvation of carbocations is presented. This procedure is based on Marcus Theory (MT) and the popular B3LYP/6-31G(d)// PCM method, and it allows the easy, accurate and inexpensive prediction of these barriers for carbocations of very different stability. This method was validated by the fair mean absolute error (ca. 1.5 kcal mol1 ) achieved in the prediction of 19 known experimental barriers covering a range of ca. 50 kcal mol1 . Interestingly, the new procedure also uses an original method for the calculation of the required inner reorganization energy (Li ) and free energy of reaction (DG). This procedure should pave the way to face computationally the pivotal issue of carbocation chemistry and could be easily extended to any bimolecular organic reaction.
PB Royal Society of Chemistry
SN 1463-9076
YR 2023
FD 2023
LK https://hdl.handle.net/20.500.14352/105752
UL https://hdl.handle.net/20.500.14352/105752
LA eng
NO Martínez, A. G.; Siehl, H.-U.; De La Moya, S.; Gómez, P. C. Easy and Accurate Computation of Energy Barriers for Carbocation Solvation: An Expeditious Tool to Face Carbocation Chemistry. Phys. Chem. Chem. Phys. 2023, 25 (45), 31012–31019. https://doi.org/10.1039/D3CP03544A.
NO 2023 Acuerdo transformativo financiado por la CRUE
NO Ministerio de Ciencia e Innovación (España)
NO Universidad Complutense de Madrid
DS Docta Complutense
RD 1 sept 2024