In pKa computational determination, the challenge in exploring and fostering new methodologies and approaches goes in parallel with the amelioration of computational performances. In this paper a "ready to use methodology" has been compared to other strategies, such as the re-shaping in solvation cavity (Bondi radius re-shaping), wanting to assess its reliability in predicting the pKa of a broad list of carboxylic acids. Thus, the functionals B3LYP and CAM-B3LYP have been selected, using SMD as continuum solvation model. Exploiting our previous results, two water molecules were made explicit on the reaction centre. Data show that our model (CAM-B3LYP/2H2 O) is capable to accurately predict pKa, leading to mean absolute error (MAE) values lower than 0.5. Noteworthy, good results were achieved in computing the pKa of substituents bearing nitro and cyano groups. Focusing on B3LYP, eventually remarkable outputs were obtained only when Bondi correction was applied to the complex with two water molecules. Hence, massive outcomes were obtained in foreseeing the trichloro and trifluoro acetic acid pKa. These findings demonstrated that no complex level of theory nor external factor is required to accurately predict carboxylic acids pKa, with MAE well below 0.5 units.

Pezzola, S., Venanzi, M., Galloni, P., Conte, V., Sabuzi, F. (2023). Easy to use DFT approach for computational pKa determination of carboxylic acids. CHEMISTRY [10.1002/chem.202303167].

Easy to use DFT approach for computational pKa determination of carboxylic acids

Pezzola, Silvia;Venanzi, Mariano;Galloni, Pierluca;Conte, Valeria;Sabuzi, Federica
2023-10-30

Abstract

In pKa computational determination, the challenge in exploring and fostering new methodologies and approaches goes in parallel with the amelioration of computational performances. In this paper a "ready to use methodology" has been compared to other strategies, such as the re-shaping in solvation cavity (Bondi radius re-shaping), wanting to assess its reliability in predicting the pKa of a broad list of carboxylic acids. Thus, the functionals B3LYP and CAM-B3LYP have been selected, using SMD as continuum solvation model. Exploiting our previous results, two water molecules were made explicit on the reaction centre. Data show that our model (CAM-B3LYP/2H2 O) is capable to accurately predict pKa, leading to mean absolute error (MAE) values lower than 0.5. Noteworthy, good results were achieved in computing the pKa of substituents bearing nitro and cyano groups. Focusing on B3LYP, eventually remarkable outputs were obtained only when Bondi correction was applied to the complex with two water molecules. Hence, massive outcomes were obtained in foreseeing the trichloro and trifluoro acetic acid pKa. These findings demonstrated that no complex level of theory nor external factor is required to accurately predict carboxylic acids pKa, with MAE well below 0.5 units.
30-ott-2023
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/06
English
Con Impact Factor ISI
CAM-B3LYP
DFT
Solvation Model based on Density (SMD)
carboxylic acid
computational pKa
pKa
Pezzola, S., Venanzi, M., Galloni, P., Conte, V., Sabuzi, F. (2023). Easy to use DFT approach for computational pKa determination of carboxylic acids. CHEMISTRY [10.1002/chem.202303167].
Pezzola, S; Venanzi, M; Galloni, P; Conte, V; Sabuzi, F
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/345683
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