Multiple hydrogen-bonded dimers: are only the frontier atoms relevant?

Abstract

Non-frontier atom exchanges in hydrogen-bonded aromatic dimers can induce significant interaction energy changes (up to 6.5 kcal mol⁻¹). Our quantum-chemical analyses reveal that the relative hydrogen-bond strengths of N-edited guanine–cytosine base pair isosteres, which cannot be explained from the frontier atoms, follow from the charge accumulation in the monomers.