Assessment of various density functionals and solvation models to describe acid-base,spectral and complexing properties of thiobarbituric and barbituric acids in aqueous solution

Abstract

The current research deal with ab initio calculations of equilibrium constants of stability or dissociation and some spectral properties of 2-thiobarbituric and barbituric acids. 11 DFT functionals (revTPSS, TPSSh, PBE, revPBE, M06-L, M06, M06-2X, M05-2X, M06-HF, CAM-B3LYP, X3LYP) with cc-pVDZ basis set were used for calculations of $\rm pK_{\rm a,1}$ and $\rm pK_{\rm a,2}$ . For each of functionals the calculations were carried out for three solvation models – SMD, COSMO and C-PCM. It has been found that functionals containing 55% Hartree-Fock exchange (M06-2X and M05-2X) provide a better approach. The TD-DFT calculations show that revTPSS and TPSSh give accurate results for the description of the spectral characteristics. The revTPSS/CRNBL ECP/SMD level was tested for evaluating parameters of complex formation process these acids with La(III) for various computational models.

Keywords

Barbituric acid thiobarbituric acid DFT TD-DFT

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