Calculation of VS,max and Its Use as a Descriptor for the Theoretical Calculation of pKa Values for Carboxylic Acids
The theoretical calculation of pKa values for Brønsted acids is a challenging task that involves sophisticated and time-consuming methods. Therefore, heuristic approaches are efficient and appealing methodologies to approximate these values. Herein, we used the maximum surface electrostat...
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doaj-6d78f7bed6974de28389ffec57424edf2020-11-25T00:41:54ZengMDPI AGMolecules1420-30492018-12-012417910.3390/molecules24010079molecules24010079Calculation of VS,max and Its Use as a Descriptor for the Theoretical Calculation of pKa Values for Carboxylic AcidsGuillermo Caballero-García0Gustavo Mondragón-Solórzano1Raúl Torres-Cadena2Marco Díaz-García3Jacinto Sandoval-Lira4Joaquín Barroso-Flores5Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Unidad San Cayetano, Carretera Toluca–Atlacomulco km 14.5, Personal de la UNAM, Toluca 50200, MexicoCentro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Unidad San Cayetano, Carretera Toluca–Atlacomulco km 14.5, Personal de la UNAM, Toluca 50200, MexicoCentro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Unidad San Cayetano, Carretera Toluca–Atlacomulco km 14.5, Personal de la UNAM, Toluca 50200, MexicoCentro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Unidad San Cayetano, Carretera Toluca–Atlacomulco km 14.5, Personal de la UNAM, Toluca 50200, MexicoCentro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Unidad San Cayetano, Carretera Toluca–Atlacomulco km 14.5, Personal de la UNAM, Toluca 50200, MexicoCentro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Unidad San Cayetano, Carretera Toluca–Atlacomulco km 14.5, Personal de la UNAM, Toluca 50200, MexicoThe theoretical calculation of pKa values for Brønsted acids is a challenging task that involves sophisticated and time-consuming methods. Therefore, heuristic approaches are efficient and appealing methodologies to approximate these values. Herein, we used the maximum surface electrostatic potential (VS,max) on the acidic hydrogen atoms of carboxylic acids to describe the H-bond interaction with water (the same descriptor that is used to characterize σ-bonded complexes) and correlate the results with experimental pKa values to obtain a predictive model for other carboxylic acids. We benchmarked six different methods, all including an implicit solvation model (water): Five density functionals and the Møller–Plesset second order perturbation theory in combination with six different basis sets for a total of thirty-six levels of theory. The ωB97X-D/cc-pVDZ level of theory stood out as the best one for consistently reproducing the reported pKa values, with a predictive power of 98% correlation in a test set of ten other carboxylic acids.http://www.mdpi.com/1420-3049/24/1/79pKahydrogen bondmaximum surface potentialσ–hole |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Guillermo Caballero-García Gustavo Mondragón-Solórzano Raúl Torres-Cadena Marco Díaz-García Jacinto Sandoval-Lira Joaquín Barroso-Flores |
spellingShingle |
Guillermo Caballero-García Gustavo Mondragón-Solórzano Raúl Torres-Cadena Marco Díaz-García Jacinto Sandoval-Lira Joaquín Barroso-Flores Calculation of VS,max and Its Use as a Descriptor for the Theoretical Calculation of pKa Values for Carboxylic Acids Molecules pKa hydrogen bond maximum surface potential σ–hole |
author_facet |
Guillermo Caballero-García Gustavo Mondragón-Solórzano Raúl Torres-Cadena Marco Díaz-García Jacinto Sandoval-Lira Joaquín Barroso-Flores |
author_sort |
Guillermo Caballero-García |
title |
Calculation of VS,max and Its Use as a Descriptor for the Theoretical Calculation of pKa Values for Carboxylic Acids |
title_short |
Calculation of VS,max and Its Use as a Descriptor for the Theoretical Calculation of pKa Values for Carboxylic Acids |
title_full |
Calculation of VS,max and Its Use as a Descriptor for the Theoretical Calculation of pKa Values for Carboxylic Acids |
title_fullStr |
Calculation of VS,max and Its Use as a Descriptor for the Theoretical Calculation of pKa Values for Carboxylic Acids |
title_full_unstemmed |
Calculation of VS,max and Its Use as a Descriptor for the Theoretical Calculation of pKa Values for Carboxylic Acids |
title_sort |
calculation of vs,max and its use as a descriptor for the theoretical calculation of pka values for carboxylic acids |
publisher |
MDPI AG |
series |
Molecules |
issn |
1420-3049 |
publishDate |
2018-12-01 |
description |
The theoretical calculation of pKa values for Brønsted acids is a challenging task that involves sophisticated and time-consuming methods. Therefore, heuristic approaches are efficient and appealing methodologies to approximate these values. Herein, we used the maximum surface electrostatic potential (VS,max) on the acidic hydrogen atoms of carboxylic acids to describe the H-bond interaction with water (the same descriptor that is used to characterize σ-bonded complexes) and correlate the results with experimental pKa values to obtain a predictive model for other carboxylic acids. We benchmarked six different methods, all including an implicit solvation model (water): Five density functionals and the Møller–Plesset second order perturbation theory in combination with six different basis sets for a total of thirty-six levels of theory. The ωB97X-D/cc-pVDZ level of theory stood out as the best one for consistently reproducing the reported pKa values, with a predictive power of 98% correlation in a test set of ten other carboxylic acids. |
topic |
pKa hydrogen bond maximum surface potential σ–hole |
url |
http://www.mdpi.com/1420-3049/24/1/79 |
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