What can be learned from femtochemistry: the H bond in water

A non-empirical theory is presented showing how infrared pump–probe spectroscopy can be used to measure subpicosecond variations of the oxygen–oxygen distribution functions in liquid water, Δg(r, τ). It should be emphasised that the equations derived in the present contribution are exact up to the second order in the perturbation expansion. These equations are model independent and provide a route to predict time-dependent radial distribution functions that are measured by time-resolved X-ray when the out-of-equilibrium configuration is produced by an optical pump pulse. It is shown that the profiles of OH stretching bands of HDO/D₂O can be brought into a full coincidence with Δg(r, τ). We thus prove that femtosecond pump–probe experiments are indeed useful to measure the time dependency of a H bond length. The theoretical framework developed in the present contribution is applicable to any H bonded system and especially to the field of bio-molecules or bio-system where H bonds play a key role in the unfolding/folding mechanism.