Better performance of Hartree-Fock over DFT: a quantum mechanical investigation on pyridinium benzimidazolate types of zwitterions in the light of localization/delocalization issues

Abstract

Context: With the advent of fast computing facilities, combined with rapid emerges of many new and intricate quantum mechanical functionals, computations with pure Hartree-Fock (HF) theory are now-a-days regarded as trivial or obsolete, or even considered as not reliable by many researchers. Consequently, current trends in computational chemistry show extensive use of post-HF theories for smaller molecular systems and various DFT methods for organic and inorganic chemistry related problems (larger molecules/systems). In this contribution, I have tried to show that sometimes, HF might be more suitable over DFT methodologies in addressing structure-property correlations. Molecules studied here were previously synthesized by Boyd in 1966 and important experimental data were produced by Alcalde and co-workers in 1987. Comparison of computed and experimental results clearly shows that HF method was more effective in reproducing the experimental data compared to especially the DFT methodologies. Reliability of HF method was further assured from the very similar results shown by the CCSD, CASSCF, CISD and QCISD methods. Current study also indicates that the localization issue associated with HF proved to be advantageous over delocalization issue of DFT based methodologies, in correctly describing the structure-property correlation for zwitterion systems.

Methods: All computations were performed with Gaussian 09. A wide-range of quantum mechanical methodologies, HF, B3LYP, CAM-B3LYP, BMK, B3PW91, TPSSh, LC-ωPBE, M06-2X, M06-HF, ωB97xD, MP2, CASSCF, CCSD, QCISD, CISD and semi-empirical methods like, Huckel, CNDO, AM1, PM3MM and PM6, were used for investigations.

Keywords: DFT; Dipole; HF; Post-HF; Zwitterion.

Scheme 1

Optimized geometry of Molecule 1 shown with available experimental crystallographic data and experimental dipole moment [35, 36]

Fig. 1

Pyridinium benzimidazolate zwitterion (Molecule 1) in its possible canonical forms, frontier molecular orbitals (HOMO & LUMO), and ESP map. Diagrams are not to scale