R-hole interactions of group IV-VII radical-containing molecules: A comparative study.

For the first time, the potentiality of the sp-hybridized group IV-VII radical (R)-containing molecules to participate in R-hole interactions was comparatively assessed using SiFPOF, SOF, and ClO models in the trigonal pyramidal geometry. In that spirit, a plethora of quantum mechanical calculations was performed at the MP2/aug-cc-pVTZ level of theory. According to the results, all the investigated R-containing molecules exhibited potent versatility to engage in R-hole … Lewis base interactions with significant negative binding energies for the NCH-based complexes. The strength of R-hole interactions was perceived to obey the ClO … > SOF … > POF … > SiF … Lewis base order, outlining an inverse correlation between the binding energy and the atomic size of the R-hole donor. Benchmarking of the binding energy at the CCSD/CBS(T) computational level was executed for all the explored interactions and addressed an obvious similarity between the MP2 and CCSD energetic findings. QTAIM analysis critically unveiled the closed-shell nature of the explored R-hole interactions. SAPT-EDA proclaimed the reciprocal contributions of electrostatic and dispersion forces to the total binding energy. These observations demonstrate in better detail the nature of R-hole interactions, leading to a convincing amelioration for versatile fields relevant to materials science and drug design.