Photochemistry of the water dimer: time-dependent quantum wave-packet description of the dynamics at the S1-S0...

The photoinduced electron-driven proton-transfer dynamics of the water-dimer system has been investigated by time-dependent quantum wave-packet calculations. The main nuclear degrees of freedom driving the system from the Frank-Condon region to the S(0)-S(1) conical intersection are the distance between the oxygen atoms and the displacement of the hydrogen atom from the oxygen-oxygen bond center. Two important coupling modes have been investigated: Rotation of the H-donating water dangling proton and asymmetric stretching of the H-accepting water dangling protons' O(a)H bonds. Potential energy surfaces of the ground and lowest excited electronic states have been constructed on the basis of ab initio calculations. The time-dependent quantum wave-packet propagation has been employed within the (2 + 1)-dimensional systems for the description of the nonadiabatic dynamics of water dimer. The effects of the initial vibrational state of the system on the electronic population transfer and dissociation dynamics are presented. To approximate the photochemical behavior of water dimer in bulk water, we add a boundary condition into the (2 + 1)-dimensional systems to simulate the existence of water bulk. The results provide insight into the mechanisms of excited state deactivation of the water-dimer system in gas phase and in bulk water through the electron-driven proton-transfer process.