Modelling proton tunnelling in the adenine-thymine base pair

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...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2015-05, Vol.17 (19), p.1334-1344
Main Authors: Godbeer, A. D, Al-Khalili, J. S, Stevenson, P. D
Format: Article
Language:English
Subjects:
Adenine - chemistry
Base Pairing
Density
Hydrogen Bonding
Mathematical analysis
Mathematical models
Models, Molecular
Potential energy
Protons
Quantum Theory
Quantum tunnelling
Searching
Tautomers
Thermodynamics
Thymine - chemistry
Time Factors
Tunnelling
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Summary: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. Environment-assisted quantum tunnelling is unlikely to play a significant role in adenine-thymine tautomerisation.
ISSN:1463-9076
1463-9084
DOI:10.1039/c5cp00472a