Observation of electronic coherence created at conical intersections and its decoherence in aqueous solution

Electronic quantum coherence is a prerequisite for charge migration in molecules and emerging molecular quantum technologies. It also underlies new forms of spectroscopy and can enhance molecular function. Whether conical intersections can create electronic coherence and for how long electronic coherence can survive in aqueous environments has remained elusive and controversial, respectively. Here, we use X-ray spectroscopy to realize a breakthrough on both of these topics. We find that electronic relaxation from the $^1$B$_{2\rm{u}}$($\pi\pi^*$) state of pyrazine through conical intersections (CIs) induces previously unobserved electronic and vibrational quantum coherences between the $^1$B$_{3\rm{u}}$(n$\pi^*$) and $^1$A$_{\rm{u}}$(n$\pi^*$) states in the gas phase, which correspond to an electronic ring current. These coherences are entirely suppressed when pyrazine is dissolved in water. These observations, supported by the latest advances in multiconfigurational electronic-structure calculations and non-adiabatic dynamics simulations, confirm that CIs can create electronic coherences and that aqueous solvation can decohere them in less than 40 fs. This study opens the door to the investigation of the broad class of electronic coherences created during light-induced molecular dynamics and to quantify their susceptibility to aqueous solvation.
Comment: 54 pages, 28 figures