Negative Dissociation Energy Phenomenon of Metastable H-Bonds As Revealed in Triplex DNA Hole Migration

摘要: Ab initio calculations reveal an unknown energetic phenomenon for H-bonds in the hole-trapping triplex C p •G ° motif observed experimentally hole migration which can explain lower but really available oxidization possibility site. Hole trapping considerably destabilize unit and lead to unexpected barrier-hindered channel with a negative dissociation energy. This is governed by balance between electrostatic repulsion H-bonding attraction two associated moieties different attenuations of opposite interactions respect H-bond distance. be viewed as high-energy node DNA wire modulates into or through it via its unusual energetics. It provides useful information understanding type complicated intermolecular interactions, novel "high-energy" bond, applied further interpret hidden transport properties energy conversion/transfer mechanisms related fields.