Transient absorption of vibrationally excited water

We study the spectral response of the transition between the first and the second excited state of the O-H stretch vibration of HDO dissolved in liquid D2O with two-color femtosecond mid-infrared spectroscopy. The spectral response of this transition differs strongly from the fundamental absorption spectrum of the O-H stretch vibration. In addition, excitation of the O-H stretch vibration is observed to lead to a change of the hydrogen-bond dynamics of liquid water. We show that both these observations can be described with a refined quantum-mechanical version of the Lippincott-Schroeder model for hydrogen-bonded OH...O systems. (C) 2002 American Institute of Physics.