Abstract

Transient resonance Raman spectra of T 1 benzophenone (BP) and its carbonyl- 18O-substituted analogue were measured with 355 nm excitation which is in resonance with a triplet-triplet (T n ←T 1) transition in the ultraviolet. The intensity of the CO stretch band was greatly enhanced under this resonance condition. Reliable values of the T 1 CO stretching frequency were obtained including the solvent shifts. It is concluded that the solvent dependence of the photochemical reactivity of BP is not primarily due to the solvent-induced structural changes in the T 1 state. The character of the two different T-T transitions (T n ←T 1 and T n ←T 1) is discussed in relation to the observed Raman spectral changes with different resonance conditions.

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