Flickering dipoles in the gas phase: Structures, internal dynamics, and dipole moments of -naphthol-H2O in its ground and excited electronic states

Adam J. Fleisher, Justin W. Young, David W. Pratt, Alessandro Cembran, Jiali Gao

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Abstract

Described here are the rotationally resolved S1-S0 electronic spectra of the acid-base complex cis - naphthol-H2O in the gas phase, both in the presence and absence of an applied electric field. The data show that the complex has a trans-linear O - HO hydrogen bond configuration involving the -OH group of cis - naphthol and the oxygen lone pairs of the attached water molecule in both electronic states. The measured permanent electric dipole moments of the complex are 4.00 and 4.66 D in the S0 and S1 states, respectively. These reveal a small amount of photoinduced charge transfer between solute and solvent, as supported by density functional theory calculations and an energy decomposition analysis. The water molecule also was found to tunnel through a barrier to internal motion nearly equal in energy to kT at room temperature. The resulting large angular jumps in solvent orientation produce flickering dipoles that are recognized as being important to the dynamics of bulk water.

Original languageEnglish (US)
Article number114304
JournalJournal of Chemical Physics
Volume134
Issue number11
DOIs
StatePublished - Mar 21 2011

Bibliographical note

Funding Information:
We acknowledge the help of Philip J. Morgan during the trans-2HN experiments, David F. Plusquellic for JB95 fitting program updates, and the National Science Foundation (NSF) for funding (CHE-0911117). A.J.F. also acknowledges support from the Andrew Mellon Predoctoral Fellowship Program at the University of Pittsburgh.

Copyright:
Copyright 2011 Elsevier B.V., All rights reserved.

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