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Modelling proton tunnelling in the adenine-thymine base pair.

Godbeer, AD, Al-Khalili, JS and Stevenson, PD (2015) Modelling proton tunnelling in the adenine-thymine base pair. Phys Chem Chem Phys, 17 (19). pp. 13034-13044.

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Abstract

The energies of the canonical (standard, amino-keto) and tautomeric (non-standard, imino-enol) charge-neutral forms of the adenine-thymine base pair (A-T and A*-T*, respectively) are calculated using density functional theory. The reaction pathway is then computed using a transition state search to provide the asymmetric double-well potential minima along with the barrier height and shape, which are combined to create the potential energy surface using a polynomial fit. The influence of quantum tunnelling on proton transfer within a base pair H-bond (modelled as the DFT deduced double-well potential) is then investigated by solving the time-dependent master equation for the density matrix. The effect on a quantum system by its surrounding water molecules is explored via the inclusion of a dissipative Lindblad term in the master equation, in which the environment is modelled as a heat bath of harmonic oscillators. It is found that quantum tunnelling, due to transitions to higher energy eigenstates with significant amplitudes in the shallow (tautomeric) side of the potential, is unlikely to be a significant mechanism for the creation of adenine-thymine tautomers within DNA, with thermally assisted coupling of the environment only able to boost the tunnelling probability to a maximum of 2 × 10(-9). This is barely increased for different choices of the starting wave function or when the geometry of the potential energy surface is varied.

Item Type: Article
Authors :
AuthorsEmailORCID
Godbeer, ADUNSPECIFIEDUNSPECIFIED
Al-Khalili, JSUNSPECIFIEDUNSPECIFIED
Stevenson, PDUNSPECIFIEDUNSPECIFIED
Date : 6 May 2015
Identification Number : https://doi.org/10.1039/c5cp00472a
Related URLs :
Depositing User : Symplectic Elements
Date Deposited : 28 Mar 2017 10:53
Last Modified : 28 Mar 2017 10:53
URI: http://epubs.surrey.ac.uk/id/eprint/807650

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