High resolution electronic spectra of anisole and anisole-water in the gas phase: hydrogen bond switching in the S1 state.

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.