Direct Evidence of Angular Jumps During Water Reorientation Through Two-Dimensional Infrared Anisotropy

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TitreDirect Evidence of Angular Jumps During Water Reorientation Through Two-Dimensional Infrared Anisotropy
Type de publicationJournal Article
Nouvelles publications2010
AuteursStirnemann G, Laage D
JournalJournal of Physical Chemistry Letters
Volume1
Fascicule10
Pagination1511-1516
Année de publicationMay
Numéro1948-7185
Accession NumberISI:000277976400001
Résumé

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.

URL<Go to ISI>://000277976400001
DOI10.1021/jz100385r
Importer un fichierDirect Evidence of Angular Jumps During Water Reorientation Through Two-Dimensional Infrared Anisotropy
Unité de rattachement: 
UMR 8640