@article {2010|1696, title = {Direct evidence of angular jumps during water reorientation through two-dimensional infrared anisotropy}, journal = {J. Phys. Chem. Lett.}, volume = {1}, year = {2010}, pages = {1511{\textendash}1516}, abstract = {

Water reorientation was recently suggested via simulations to proceed through large angular jumps, but direct experimental evidence has so far remained elusive. Here we show that both infrared pump-probe and photon echo spectroscopies can provide such evidence through the measurement of the two-dimensional anisotropy decay. We calculate these two-dimensional anisotropies from simulations and show they can be interpreted as a vibrational frequency-dependent resolved orientation time-correlation function. We develop a frequency-dependent extended jump model to predict the nature of the angular jump signature in these anisotropies. This model provides a rigorous and unambiguous connection between ultrafast infrared experimental results and the presence of angular jumps in bulk water, and calls for new experiments.

}, issn = {19487185}, doi = {10.1021/jz100385r}, author = {Guillaume Stirnemann and Laage, Damien} }