Solvent Effects on Ultrafast Charge Transfer Population: Insights from the Quantum Dynamics of Guanine‐Cytosine in Chloroform

We study the ultrafast photoactivated dynamics of the hydrogen bonded dimer Guanine‐Cytosine in chloroform solution, focusing on the population of the Guanine→Cytosine charge transfer state (GC‐CT), an important elementary process for the photophysics and photochemistry of nucleic acids. We integrate a quantum dynamics propagation scheme, based on a linear vibronic model parameterized through time dependent density functional theory calculations, with four different solvation models, either implicit or explicit. On average, after 50 fs, 30∼40 % of the bright excited state population has been transferred to GC‐CT. This process is thus fast and effective, especially when transferring from the Guanine bright excited states, in line with the available experimental studies. Independent of the adopted solvation model, the population of GC‐CT is however disfavoured in solution with respect to the gas phase. We show that dynamical solvation effects are responsible for this puzzling result and assess the different chemical‐physical effects modulating the population of CT states on the ultrafast time‐scale. We also propose some simple analyses to predict how solvent can affect the population transfer between bright and CT states, showing that the effect of the solute/solvent electrostatic interactions on the energy of the CT state can provide a rather reliable indication of its possible population. Quantum Dynamical simulations predict that, following UV irradiation of the Guanine‐Cytosine Watson‐Crick pair in chloroform, 20∼50 % of the photoexcited population decays to a Gua→Cyt Charge Transfer state within 100 fs. Different solvation models were used in an attempt to define the effects modulating this population transfer and to explain why it is less effective than in the gas phase.”