title: Enol tautomers of Watson-Crick base pair models are metastable because of nuclear quantum effects.
abstract: Intermolecular enol tautomers of Watson-Crick base pairs could emerge spontaneously via interbase double proton transfer. It has been hypothesized that their formation could be facilitated by thermal fluctuations and proton tunneling, and possibly be relevant to DNA damage. Theoretical and computational studies, assuming classical nuclei, have confirmed the dynamic stability of these rare tautomers. However, by accounting for nuclear quantum effects explicitly through Car-Parrinello path integral molecular dynamics calculations, we find the tautomeric enol form to be dynamically metastable, with lifetimes too insignificant to be implicated in DNA damage.
authors.affiliation: Department of Chemistry, New York University, New York, New York 10003, USA.
authors.forename: Alejandro
authors.initials: A
authors.lastname: Pérez
authors.forename: Mark E
authors.initials: ME
authors.lastname: Tuckerman
authors.forename: Harold P
authors.initials: HP
authors.lastname: Hjalmarson
authors.forename: O Anatole
authors.initials: OA
authors.lastname: von Lilienfeld
mesh_terms: D020029:Base Pairing; D004247:DNA / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory
chemical_list: D007659:Ketones; D004247:DNA