Computed vs Experimental Energy Barriers in Solution: Influence of the type of the density functional approximation. DOI Creative Commons

Aurore E. F. Denjean,

Jordan Rio, Ilaria Ciofini

et al.

Published: March 20, 2024

Mechanistic investigations at the Density Functional Theory (DFT) level of organic and organometallic reactions in solution are now broadly accessible routinely implemented to complement experimental investigations. The selection an appropriate functional among plethora developed ones is first challenge on way reliable energy barrier calculations. To provide guidelines for choice initial computational level, performances commonly used non-empirical (PBE, PBE0, PBE0-DH) empirical density functionals (BLYP, B3LYP, B2PLYP) were evaluated relative activation enthalpies. Most reactivity databases assess primarily based high calculations, here a set enthalpies performed selected from literature. As general trend, outperform ones. most accurate barriers obtained with hybride PBE0 double-hybrid PBE0-DH functionals, both providing similar performance. Regardless under consideration, addition GD3-BJ dispersion correction does not enhance accuracy computed barriers.

Language: Английский

Computed vs Experimental Energy Barriers in Solution: Influence of the type of the density functional approximation. DOI Creative Commons

Aurore E. F. Denjean,

Jordan Rio, Ilaria Ciofini

et al.

Published: March 20, 2024

Mechanistic investigations at the Density Functional Theory (DFT) level of organic and organometallic reactions in solution are now broadly accessible routinely implemented to complement experimental investigations. The selection an appropriate functional among plethora developed ones is first challenge on way reliable energy barrier calculations. To provide guidelines for choice initial computational level, performances commonly used non-empirical (PBE, PBE0, PBE0-DH) empirical density functionals (BLYP, B3LYP, B2PLYP) were evaluated relative activation enthalpies. Most reactivity databases assess primarily based high calculations, here a set enthalpies performed selected from literature. As general trend, outperform ones. most accurate barriers obtained with hybride PBE0 double-hybrid PBE0-DH functionals, both providing similar performance. Regardless under consideration, addition GD3-BJ dispersion correction does not enhance accuracy computed barriers.

Language: Английский

Citations

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