期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 109, 期 5, 页码 767-772出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp046004y
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The rotationally resolved S-1 <-- S-0 electronic spectrum of the water complex of p-difluorobenzene (pDFB) has been observed in the collision-free environment of a molecular beam. Analyses of these data show that water forms a planar a-bonded complex with pDFB via two points of attachment, a stronger F --- H-O hydrogen bond and weaker H --- O-H hydrogen bond, involving an ortho hydrogen atom of the ring. Despite the apparent rigidity of this structure, the water molecule also is observed to move within the complex, leading to a splitting of the spectrum into two tunneling subbands. Analyses of these data show that this motion is a combined inversion-internal rotation of the attached water, analogous to the acceptor-switching motion in the water dimer. The barriers to this motion are significantly different in the two electronic states owing to changes in the relative strengths of the two hydrogen bonds that hold the complex together.
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