A computational study on the characteristics of open-shell H-bonding interaction between carbamic acid (NHCOOH) and HO, HOS or HSO radicals.

Quantum chemical computations were applied to investigate the characteristics of open-shell hydrogen-bonding interactions in the complexes of carbamic acid (NHCOOH, CA) with HO, HOS and HSO radicals. All the resulting complexes were studied using the MP2, B3PW91 and B3LYP computational levels and 6311++G** basis set. Geometry optimizations show that the O-H⋯O contact is stronger than N-H⋯O and S-H⋯O. The interaction energies revealed that all the radicals form stronger hydrogen bonded complexes at site-1, as confirmed by electron-density (ρ) and corresponding Laplacian (∇ρ) values obtained by atoms in molecule (AIM) analysis. Non-covalent interaction and reduced density gradient analysis support the AIM results. Natural bond orbital analysis was employed to obtain the stabilization energies (E) due to charge delocalization between the interacting units. Energy decomposition analysis suggests that, for the title complexes, the exchange energy makes a larger contribution to the total interaction energy compared to other energy terms. Graphical abstract Open-shell H-bondinginteraction between carbamic acid (NHCOOH) and HO, HOS or HSOradicals.