| Popis: |
We have explored the proposition that emission from bound orbiting states of aromatic van der Waals complexes occurs where the free aromatic emits. Pumping 6 1 ¯ in benzene–Ar is predicted to lead, via intramolecular vibrational energy redistribution (IVR), to excitation in van der Waals modes associated with 16 1 ¯ that are above the barrier to bound orbital motion. The 6 1 ¯ dispersed fluorescence spectrum shows a red-shaded, broad band with a maximum 21 cm −1 to the blue of the expected 6 1 0 16 1 1 ¯ transition, where the 6 1 0 16 1 1 band of free benzene occurs. The time dependence of the parent and growth bands in the 6 1 ¯ spectrum suggests that IVR from this level is reversible. |
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