Title | Direct evidence of angular jumps during water reorientation through two-dimensional infrared anisotropy |
Publication Type | Journal Article |
Year of Publication | 2010 |
Authors | Stirnemann G, Laage D |
Journal | J. Phys. Chem. Lett. |
Volume | 1 |
Pagination | 1511–1516 |
ISSN | 19487185 |
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. |
DOI | 10.1021/jz100385r |
Citation Key | 2010|1696 |