RT Journal Article
T1 Role of Microsolvation and Quantum Effects in the Accurate Prediction of Kinetic Isotope Effects: The Case of Hydrogen Atom Abstraction in Ethanol by Atomic Hydrogen in Aqueous Solution
A1 Kannath, Suraj
A1 Adamczyk, Paweł
A1 Ferro Costas, David
A1 Fernández Ramos, Antonio
A1 Major, Dan Thomas
A1 Dybała-Defratyka, Agnieszka
K1 Kinetic parameters
K1 Transition states
K1 Molecular modeling
K1 Solvation
K1 Molecules
AB Hydrogen abstraction from ethanol by atomic hydrogen in aqueous solution is studied using two theoretical approaches: the multipath variational transition state theory (MP-VTST) and a path-integral formalism in combination with free-energy perturbation and umbrella sampling (PI-FEP/UM). The performance of the models is compared to experimental values of H kinetic isotope effects (KIE). Solvation models used in this study ranged from purely implicit, via mixed–microsolvation treated quantum mechanically via the density functional theory (DFT) to fully explicit representation of the solvent, which was incorporated using a combined quantum mechanical-molecular mechanical (QM/MM) potential. The effects of the transition state conformation and the position of microsolvating water molecules interacting with the solute on the KIE are discussed. The KIEs are in good agreement with experiment when MP-VTST is used together with a model that includes microsolvation of the polar part of ethanol by five or six water molecules, emphasizing the importance of explicit solvation in KIE calculations. Both, MP-VTST and PI-FEP/UM enable detailed characterization of nuclear quantum effects accompanying the hydrogen atom transfer reaction in aqueous solution
PB American Chemical Society
SN 1549-9618
YR 2020
FD 2020
LK http://hdl.handle.net/10347/24326
UL http://hdl.handle.net/10347/24326
LA eng
NO J. Chem. Theory Comput. 2020, 16, 2, 847–859
NO This work was partially supported by the National Science Center in Poland (Sonata BIS grant UMO-2014/14/E/ST4/00041) and in part by PLGrid Infrastructure (Poland). S.K. acknowledges the Erasmus+ programme within which his 3-month project conducted at the University of Santiago de Compostela was possible. A.F-.R. thanks the Consellería de Cultura, Educación e Ordenación Universitaria (Axuda para Consolidación e Estructuración de unidades de investigación competitivas do Sistema Universitario de Galicia, Xunta de Galicia ED431C 2017/17 & Centro singular de investigación de Galicia acreditación 2016-2019, ED431G/09) and the European Regional Development Fund (ERDF). D.F-.C. also thanks Xunta de Galicia for financial support through a postdoctoral grant
DS Minerva
RD 28 abr 2026