Pathways for H2O Bend Vibrational Relaxation in Liquid Water

The mechanism of the H2O bend vibrational relaxation in liquid water has been examined via classical MID simulations and an analysis of work and power contributions. The relaxation is found to be dominated by energy flow to the hindered rotation of the bend excited water molecule. This energy transfer, representing approximately 2/3 of the transferred energy, is due to a 2:1 Fermi resonance for the centrifugal Coupling between the water bend and rotation. The remaining energy flow (similar to 1/3) from the excited water bend is dominated by transfer to the excited water molecule's first four water neighbors, i.e., the first hydration shell, and is itself dominated by energy flow to the two water molecules hydrogen (H)-bonded to the hydrogens of the central H2O. The energy flow from the produced rotationally excited central molecule is less local in character, with approximately half of its rotational kinetic energy being transferred to water molecules Outside of the first hydration shell, whereas the remaining half is preferentially transferred to the two first hydration shell water molecules donating H-bonds to the central water oxygen. The overall energy flow is well described by an approximate kinetic scheme.