Binding energies and interaction origins between nonclassical single-electron hydrogen, sodium and lithium bonds and neutral boron-containing radicals: a theoretical investigation

Abstract

Nonclassical single electron hydrogen, sodium and lithium bonds (SEHBs, SENaBs and SELiBs) between single electron acceptors X–A (A=H, Na, Li; X=CN, HCC, HO, NC, CF3) and neutral radicals BY2 (Y=H, OH, CH3) and have been systematically investigated by high level theoretical methods, such as second-order Moller-Plesset perturbation theory (MP2), spin-component-scaled Moller-Plesset theory (SCS-MP2), the coupled cluster method with perturbative triples (CCSD(T)), and the correlation consistent composite approach (ccCA). Binding energies have been corrected for zero-point vibrational effects and (when applicable) basis set superposition error. The quantum theory of atoms in molecules (AIM) and natural bond orbital (NBO) analyses were also employed to qualitatively characterize the single electron bond interactions. The stabilization energy was partitioned via the localized molecular orbital energy decomposition analysis (LMO-EDA) method, and both electrostatic and exchange interactions were seen to be major driving forces for the complex stabilization. Interestingly, the sum of the energy contributors of exchange (EEX), repulsion (EREP), polarization (EPOL), dispersion (EDIS) is close to zero and the changes in the interaction energy follow the trend of the electrostatic energy (EES). We observe several linear relationships among the optimized intermolecular parameters and the interaction energies of the various complexes.