title: Inverse Temperature Dependence of Nuclear Quantum Effects in DNA Base Pairs.
abstract: Despite the inherently quantum mechanical nature of hydrogen bonding, it is unclear how nuclear quantum effects (NQEs) alter the strengths of hydrogen bonds. With this in mind, we use ab initio path integral molecular dynamics to determine the absolute contribution of NQEs to the binding in DNA base pair complexes, arguably the most important hydrogen-bonded systems of all. We find that depending on the temperature, NQEs can either strengthen or weaken the binding within the hydrogen-bonded complexes. As a somewhat counterintuitive consequence, NQEs can have a smaller impact on hydrogen bond strengths at cryogenic temperatures than at room temperature. We rationalize this in terms of a competition of NQEs between low-frequency and high-frequency vibrational modes. Extending this idea, we also propose a simple model to predict the temperature dependence of NQEs on hydrogen bond strengths in general.
authors.forename: Wei
authors.initials: W
authors.lastname: Fang
authors.forename: Ji
authors.initials: J
authors.lastname: Chen
authors.affiliation: Physical and Theoretical Chemistry Lab, University of Oxford , South Parks Road, OX1 3QZ Oxford, United Kingdom.
authors.forename: Mariana
authors.initials: M
authors.lastname: Rossi
authors.affiliation: School of Physics and Electronics, Hunan University , Changsha 410082, People's Republic of China.
authors.forename: Yexin
authors.initials: Y
authors.lastname: Feng
authors.affiliation: International Center for Quantum Materials, School of Physics and Collaborative Innovation Center of Quantum Matter, Peking University , Beijing 100871, People's Republic of China.
authors.forename: Xin-Zheng
authors.initials: XZ
authors.lastname: Li
authors.forename: Angelos
authors.initials: A
authors.lastname: Michaelides
mesh_terms: D020029:Base Pairing / Q000502:physiology*; D004247:DNA / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory
chemical_list: D004247:DNA