Vibrational energy relaxation pathways of water

Vibrational energy relaxation (VR) of the OH stretch νOH and bend δH2O in water is studied by the mid-IR pump with anti-Stokes Raman probe technique. The broad νOH band in water consists of two inhomogeneously broadened subbands. VR in the larger red-shifted subband νOHR, with T1=0.55 ps, is shown to occur by the mechanism νOH→δH2O (1/3) and νOH → ground state (2/3). VR in the smaller longer-lived blue-shifted subband νOHB, with T1=0.75 ps, occurs by the mechanism νOH → ground state. The bending fundamental δH2O decays directly to the ground state with T1=1.4 ps.