Time-dependent density-functional study of intermolecular Coulombic decay for 2a1 ionized water dimer.

A real-space, real-time time-dependent density functional theory with Ehrenfest dynamics is used to simulate intermolecular Coulombic decay (ICD) processes following the ionization of an inner-valence electron. The approach has the advantage of treating both nuclear and electronic motions simultaneously, allowing for the study of electronic excitation, charge transfer, ionization, and nuclear motion. Using this approach, we investigate the decay process of the 2a1 ionized state of the water dimer. For the 2a1 vacancy in the proton donor water molecule, ICD is observed in our simulations. In addition, we have identified a novel dynamical process: at the initial stage, the proton generally undergoes a back-and-forth motion. Subsequently, the system may evolve along two distinct pathways: in one, no proton transfer occurs; in the other, the proton departs again from its original position and ultimately completes the transfer process. In contrast, when the vacancy resides in the proton acceptor water molecule, no proton transfer occurs and ICD remains the sole decay channel.