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  • Title: Fingerprinting the Excited-State Dynamics in Methyl Ester and Methyl Ether Anions of Deprotonated para-Coumaric Acid.
    Author: Bull JN, Anstöter CS, Verlet JRR.
    Journal: J Phys Chem A; 2020 Mar 19; 124(11):2140-2151. PubMed ID: 32105474.
    Abstract:
    Chromophores based on the para-hydroxycinnamate moiety are widespread in the natural world, including as the photoswitching unit in photoactive yellow protein and as a sunscreen in the leaves of plants. Here, photodetachment action spectroscopy combined with frequency- and angle-resolved photoelectron imaging is used to fingerprint the excited-state dynamics over the first three bright action-absorption bands in the methyl ester anions (pCEs-) of deprotonated para-coumaric acid at a temperature of ∼300 K. The excited states associated with the action-absorption bands are classified as resonances because they are situated in the detachment continuum and are open to autodetachment. The frequency-resolved photoelectron spectrum for pCEs- indicates that all photon energies over the S1(ππ*) band lead to similar vibrational autodetachment dynamics. The S2(nπ*) band is Herzberg-Teller active and has comparable brightness to the higher lying 21(ππ*) band. The frequency-resolved photoelectron spectrum over the S2(nπ*) band indicates more efficient internal conversion to the S1(ππ*) state for photon energies resonant with the Franck-Condon modes (∼80%) compared with the Herzberg-Teller modes (∼60%). The third action-absorption band, which corresponds to excitation of the 21(ππ*) state, shows complex and photon energy-dependent dynamics, with 20-40% of photoexcited population internally converting to the S1(ππ*) state. There is also evidence for a mode-specific competition between prompt autodetachment and internal conversion on the red edge of the 21(ππ*) band. There is no evidence for recovery of the ground electronic state and statistical electron ejection (thermionic emission) following photoexcitation over any of the three action-absorption bands. The photoelectron spectra for the deprotonated methyl ether derivative (pCEt-) at photon energies over the S1(ππ*) and S2(nπ*) bands indicate diametrically opposed dynamics compared with pCEs-, namely, intense thermionic emission due to efficient recovery of the ground electronic state.
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