scholarly journals Calculation of VS,max and Its Use as a Descriptor for the Theoretical Calculation of pKa Values for Carboxylic Acids

Molecules ◽  
2018 ◽  
Vol 24 (1) ◽  
pp. 79 ◽  
Author(s):  
Guillermo Caballero-García ◽  
Gustavo Mondragón-Solórzano ◽  
Raúl Torres-Cadena ◽  
Marco Díaz-García ◽  
Jacinto Sandoval-Lira ◽  
...  
Keyword(s):  
Theoretical Calculation ◽  
Carboxylic Acids ◽  
Predictive Power ◽  
Basis Sets ◽  
Hydrogen Atoms ◽  
Pka Values ◽  
Implicit Solvation Model ◽  
Moller Plesset ◽  
Surface Electrostatic Potential ◽  
Acidic Hydrogen

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.

scholarly journals Quantification of σ–Holes and Their Use as a Descriptor for the Theoretical Calculation of pKa Values for Carboxylic Acids

2018 ◽  
Author(s):  
Guillermo Caballero-García ◽  
Gustavo Mondragón-Solórzano ◽  
Raúl Torres-Cadena ◽  
Marco Díaz-García ◽  
Jacinto Sandoval-Lira ◽  
...  
Keyword(s):  
Basis Sets ◽  
Implicit Solvent ◽  
Density Functionals ◽  
Hydrogen Atoms ◽  
Acidity Constants ◽  
Pka Values ◽  
Theoretical Approaches ◽  
Solvent Model ◽  
Acidic Hydrogen ◽  
Model Water

Theoretical approaches to calculate pKa values for Brønsted acids is a challenging task that, most of the time, involves sophisticated and time-consuming methods. Therefore, heuristic approaches are efficient and appealing methodologies to approximate these values. Herein, by considering the electrostatic potential on acidic hydrogen atoms in a similar fashion that a σ–hole is defined, we calculated the maximum surface potential, VS,max, and used it as a descriptor to correlate it with experimental acidity constants. These values were calculated using the CPCM implicit solvent model (water) with six different methods: five density functionals and the Møller–Plesset second order perturbation theory. Six different basis sets were combined with each method in order to benchmark a total of thirty-six levels of theory. Overall, 1080 calculations were performed and found to correlate with experimental data. The ωB97X-D/6-31+G(d,p) level of theory stands as the best one for consistently reproduce the reported pKa values.

Møller–Plesset perturbation theory calculations of the pKa values for a range of carboxylic acids

2006 ◽  
Vol 758 (2-3) ◽  
pp. 275-278 ◽  
Author(s):  
Mansoor Namazian ◽  
Forogh Kalantary-Fotooh ◽  
Mohammad R. Noorbala ◽  
Debra J. Searles ◽  
Michelle L. Coote
Keyword(s):  
Perturbation Theory ◽  
Carboxylic Acids ◽  
Pka Values ◽  
Moller Plesset ◽  
Plesset Perturbation Theory

Theoretical analysis of the (HNO)2, (HNO···HNS), and (HNS)2 dimers — A case of red and blue shifts of N–H stretching frequency

2010 ◽  
Vol 88 (8) ◽  
pp. 849-857 ◽  
Author(s):  
Nguyen Tien Trung ◽  
Tran Thanh Hue ◽  
Minh Tho Nguyen
Keyword(s):  
Hydrogen Bond ◽  
Quantum Chemical ◽  
Bond Formation ◽  
Blue Shift ◽  
Proton Donor ◽  
Basis Sets ◽  
Coupled Cluster ◽  
Hydrogen Bond Formation ◽  
Length Contraction ◽  
Moller Plesset

The hydrogen-bonded interactions in the simple (HNZ)2 dimers, with Z = O and S, were investigated using quantum chemical calculations with the second-order Møller–Plesset perturbation (MP2), coupled-cluster with single, double (CCSD), and triple excitations (CCSD(T)) methods in conjunction with the 6-311++G(2d,2p), aug-cc-pVDZ, and aug-cc-pVTZ basis sets. Six-membered cyclic structures were found to be stable complexes for the dimers (HNO)2, (HNS)2, and (HNO–HNS). The pair (HNS)2 has the largest complexation energy (–11 kJ/mol), and (HNO)2 the smallest one (–9 kJ/mol). A bond length contraction and a frequency blue shift of the N–H bond simultaneously occur upon hydrogen bond formation of the N–H···S type, which has rarely been observed before. The stronger the intramolecular hyperconjugation and the lower the polarization of the X–H bond involved as proton donor in the hydrogen bond, the more predominant is the formation of a blue-shifting hydrogen bond.

Estimation of pKa values for carboxylic acids, alcohols, phenols and amines using changes in the relative Gibbs free energy

2012 ◽  
Vol 313 ◽  
pp. 148-155 ◽  
Author(s):  
Yue Zeng ◽  
Xianglan Chen ◽  
Dongbo Zhao ◽  
Haitao Li ◽  
Youyu Zhang ◽  
...  
Keyword(s):  
Free Energy ◽  
Carboxylic Acids ◽  
Gibbs Free Energy ◽  
Pka Values ◽  
Relative Gibbs Free Energy

Calculation of pKa values of carboxylic acids: Application to bilirubin

2010 ◽  
Vol 947 (1-3) ◽  
pp. 76-82 ◽  
Author(s):  
Rok Borštnar ◽  
Amrita Roy Choudhury ◽  
Jernej Stare ◽  
Marjana Novič ◽  
Janez Mavri
Keyword(s):  
Carboxylic Acids ◽  
Pka Values

Quantum mechanical based approaches for predicting pKa values of carboxylic acids: evaluating the performance of different strategies

RSC Advances ◽  
2016 ◽  
Vol 6 (113) ◽  
pp. 112057-112064 ◽  
Author(s):  
Aida Mariana Rebollar-Zepeda ◽  
Annia Galano
Keyword(s):  
Carboxylic Acids ◽  
Quantum Mechanical ◽  
Pka Values ◽  
Solvent Model

The FP method is recommended for estimating pKa values of carboxylic acids for which this information is still unknown, especially in combination with the PBE0 functional (MUE = 0.26) and the SMD solvent model.

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