Direct evidence of angular jumps during water reorientation through two-dimensional infrared anisotropy

TitleDirect evidence of angular jumps during water reorientation through two-dimensional infrared anisotropy
Publication TypeJournal Article
Year of Publication2010
AuthorsStirnemann G, Laage D
JournalJ. Phys. Chem. Lett.
Volume1
Pagination1511–1516
ISSN19487185
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.

DOI10.1021/jz100385r
Citation Key2010|1696