Methodological Approach Based on Structural Parameters, Vibrational Frequencies, and MMFF94 Bond Charge Increments...

In this work, we performed a comprehensive benchmark study for the ground state of five small- and medium-sized platinum derivatives, PtH, PtCl, [PtCl₄]^2-, [Pt(NH₃)₄]²⁺, and cis-[Pt(NH₃)₂Cl₂], in the gas phase and two cisplatin polymorphs in the solid phase. The benchmark encompassed 16 density functionals, including nonhybrids, hybrids, and double hybrids. Furthermore, Hartree-Fock (HF) and Post-HF by Møller-Plesset MP2 methods were also tested. Additionally, 11 basis sets were explored, comparing relativistic all-electron and RECP approaches. Our results indicate that the methodologies best suited for predicting structural parameters do not excel in predicting vibrational frequencies and vice versa. In the context of this theoretical framework, we also examine the derivation of partial atomic charges and bond charge increments (bci) as fundamental parameters within the MMFF94 classical force field. Our results show that the partial atomic charges of CHELPG present a slight charge fluctuation in Pt for all investigated levels of theory, and this behavior reproduces well the soft acid definition for Pt²⁺, giving the best description of the chemical environment of platinum in the cisplatin complex. The average calculated bci values effectively capture the atomic charge variations in the chemical environment of Pt in the investigated species. The developed bci optimization tool, based on MMFF94, was implemented using a Python code made available at https://github.com/molmodcs/bci_solver. This methodology will be further implemented in the DockThor receptor-ligand docking program, allowing future molecular docking validations involving ligand compounds containing Pt atoms.