Electronic States and Nonradiative Decay of Cold Gas-Phase Cinnamic Acid Derivatives Studied by Laser Spectroscopy with Laser Ablation Technique.

We performed UV spectroscopy for p-coumaric acid (pCA), ferulic acid (FA), and caffeic acid (CafA) under jet-cooled gas phase conditions by using a laser ablation source. These molecules showed the S1(1ππ*) - S0 absorption in the 31500-33500 cm-1 region. Both pCA and FA exhibited sharp vibronic bands, while CafA showed only broad feature. Decay time profile of the 1ππ* state was measured by picosecond pump-probe spectroscopy, and the transient state produced through the nonradiative decay (NRD) from 1ππ* and its time profile were measured by nanosecond UV-DUV pump-probe spectroscopy. The transient state was observed for pCA and FA and assigned to the T1 state, and we concluded that the NRD process of 1ππ* is "S1(1ππ*) → 1nπ* → T1(3ππ*)" similar to those of methylcinnamate and para-substituted cinnamates such as p-hydroxy, and p-methoxy methylcinnamate. On the other hand, the transient T1 sate was not detected in CafA and its NRD route is suggested to be "S1(1ππ*) → 1πσ* → H atom elimination" similar to those of phenol and catechol. The effect of hydrogen (H)-bond on the electronic state and NRD process was investigated and it was found that the H-bonding lowers the 1ππ* energy and suppresses the NRD process for all the species.

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