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.

In this work we compare two theoretical approaches to modeling the action of the environment on an open quantum system. It is often assumed that as the temperature of the environment surrounding a quantum system increases, so does the speed of environment-induced dephasing, or decoherence (dynamical noise), and so the efficacy of processes such as quantum tunneling drops. An alternative way of viewing the action of the environment is to consider it as carrying out von Neumann-type measurements that, in the limit of continuous observation, lead to the so-called quantum Zeno effect, whereby the system is never allowed to evolve because its wave function is collapsed to its initial state with overwhelming likelihood. However, it has been established in recent years that under certain conditions quantum processes such as tunneling can actually be enhanced (thermally assisted) when the system couples to its environment, as this allows transitions to higher-energy eigenstates closer to the top of the potential barrier. Here we show that, over a specific temperature range, increasing the temperature of the heat bath to encourage such thermally induced tunneling is equivalent to increasing the frequency of a von Neumann-type measurement on the system by the environment (an anti-Zeno effect). However, this correspondence between these two independent pictures of quantum measurement breaks down above a certain limit: Increasing the frequency of measurement above this limit leads to a reversal from an anti-Zeno to a Zeno effect and the tunneling rate decreases again, whereas raising the temperature further leads to a leveling off in the tunneling probability.