1. Experimental and Computational Analysis of Para-Hydroxy Methylcinnamate following Photoexcitation
- Author
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Jack Dalton, Gareth W. Richings, Jack M. Woolley, Temitope T. Abiola, Scott Habershon, and Vasilios G. Stavros
- Subjects
gas-phase ,photochemistry ,Organic Chemistry ,Pharmaceutical Science ,ultrafast spectroscopy ,DFT ,VMI ,photophysics ,cinnamate ,Analytical Chemistry ,QD241-441 ,Chemistry (miscellaneous) ,Drug Discovery ,Molecular Medicine ,QD ,Physical and Theoretical Chemistry - Abstract
Para-hydroxy methylcinnamate is part of the cinnamate family of molecules. Experimental and computational studies have suggested conflicting non-radiative decay routes after photoexcitation to its S1(ππ*) state. One non-radiative decay route involves intersystem crossing mediated by an optically dark singlet state, whilst the other involves direct intersystem crossing to a triplet state. Furthermore, irrespective of the decay mechanism, the lifetime of the initially populated S1(ππ*) state is yet to be accurately measured. In this study, we use time-resolved ion-yield and photoelectron spectroscopies to precisely determine the S1(ππ*) lifetime for the s-cis conformer of para-hydroxy methylcinnamate, combined with time-dependent density functional theory to determine the major non-radiative decay route. We find the S1(ππ*) state lifetime of s-cis para-hydroxy methylcinnamate to be ∼2.5 picoseconds, and the major non-radiative decay route to follow the [1ππ*→1nπ*→3ππ*→S0] pathway. These results also concur with previous photodynamical studies on structurally similar molecules, such as para-coumaric acid and methylcinnamate.
- Published
- 2021
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