2024-03-28T11:09:28Zhttps://gredos.usal.es/oai/requestoai:gredos.usal.es:10366/1467642022-02-07T15:38:57Zcom_10366_138663com_10366_4512com_10366_3823col_10366_138665
Multi- and single-reference methods for the analysis of multi-state peroxidation of enolates
Ortega Álvarez, Pablo
Gil-Guerrero, Sara
Veselinova Marinova, Anzhela
Zanchet, A.
González Sánchez, Lola
García Jambrina, Pablo
Sanz-Sanz, Cristina
Triplet state
Full configuration interaction
Density functional theory
Configuration interaction
Correlation-consistent basis sets
Minimum energy path problem
Potential energy surfaces
Potential energy barrier
[EN]In spite of being spin-forbidden, some enzymes are capable of catalyzing the incorporation of O2(Σg−3Σg−3) to organic substrates without needing any cofactor. It has been established that the process followed by these enzymes starts with the deprotonation of the substrate forming an enolate. In a second stage, the peroxidation of the enolate formation occurs, a process in which the system changes its spin multiplicity from a triplet state to a singlet state. In this article, we study the addition of O2 to enolates using state-of-the-art multi-reference and single-reference methods. Our results confirm that intersystem crossing is promoted by stabilization of the singlet state along the reaction path. When multi-reference methods are used, large active spaces are required, and in this situation, semistochastic heat-bath configuration interaction emerges as a powerful method to study these multi-configurational systems and is in good agreement with PNO-LCCSD(T) when the system is well-represented by a single-configuration.
2021-06-11T08:08:48Z
2021-06-11T08:08:48Z
2021
2022-07-04
info:eu-repo/semantics/article
0021-9606
http://hdl.handle.net/10366/146764
10.1063/5.0046906
1089-7690
eng
https://doi.org/10.1063/5.0046906
Spanish Ministry of Science and Innovation: FIS2017-83473-C2-P
Spanish Ministry of Science and Innovation: PID2019-107115GB-C21
Spanish Ministry of Science and Innovation: PGC2018-096444-B-I00
Junta de Castilla y León and European Social Fund: Grant No. EDU/601/2020
Fundación Salamanca City of Culture and Knowledge (program for attracting scientific talent to Salamanca)
info:eu-repo/semantics/openAccess