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Título
Multi- and single-reference methods for the analysis of multi-state peroxidation of enolates
Autor(es)
Palabras clave
Triplet state
Full configuration interaction
Density functional theory
Configuration interaction
Correlation-consistent basis sets
Minimum energy path problem
Potential energy surfaces
Potential energy barrier
Fecha de publicación
2021
Resumen
[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.
URI
ISSN
0021-9606
DOI
10.1063/5.0046906
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- GIDM. Artículos [6]