High Resolution Electronic Spectra of Anisole and Anisole−Water in the Gas Phase: Hydrogen Bond Switching in the S1 State
The Journal of Physical Chemistry A2005Vol. 110(4), pp. 1478–1483
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Abstract
Rotationally resolved S(1)<--S(0) electronic spectra of anisole and its hydrogen bonded complex containing one water molecule have been obtained. The results provide evidence for an "in-plane" complex in which the water molecule is attached via two hydrogen bonds to the anisole molecule, a donor O-H- - -O(CH(3)) bond and an acceptor H-O- - -H(ring) bond. Analysis of the subbands that appear in the spectrum of the complex suggests that hydrogen bond "switching" occurs when the complex absorbs light. The former O-H- - -O(CH(3)) bond is stronger in the ground (S(0)) state, whereas the latter H-O- - -H(ring) bond is stronger in the excited (S(1)) state. Dynamical consequences of this phenomenon are discussed.
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