Experimental and Computational Analysis of <i>Para</i>-Hydroxy Methylcinnamate following Photoexcitation
<i>Para</i>-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 S<sub>1</sub>(ππ*) state. One non-radiative decay route involves intersy...
| Main Authors: | , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-12-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/26/24/7621 |
| _version_ | 1827670817492697088 |
|---|---|
| author | Jack Dalton Gareth W. Richings Jack M. Woolley Temitope T. Abiola Scott Habershon Vasilios G. Stavros |
| author_facet | Jack Dalton Gareth W. Richings Jack M. Woolley Temitope T. Abiola Scott Habershon Vasilios G. Stavros |
| author_sort | Jack Dalton |
| collection | DOAJ |
| description | <i>Para</i>-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 S<sub>1</sub>(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 S<sub>1</sub>(ππ*) state is yet to be accurately measured. In this study, we use time-resolved ion-yield and photoelectron spectroscopies to precisely determine the S<sub>1</sub>(ππ*) lifetime for the s-<i>cis</i> conformer of <i>para</i>-hydroxy methylcinnamate, combined with time-dependent density functional theory to determine the major non-radiative decay route. We find the S<sub>1</sub>(ππ*) state lifetime of s-<i>cis para</i>-hydroxy methylcinnamate to be ∼2.5 picoseconds, and the major non-radiative decay route to follow the [<sup>1</sup>ππ*→<sup>1</sup>nπ*→<sup>3</sup>ππ*→S<sub>0</sub>] pathway. These results also concur with previous photodynamical studies on structurally similar molecules, such as <i>para</i>-coumaric acid and methylcinnamate. |
| first_indexed | 2024-03-10T03:28:23Z |
| format | Article |
| id | doaj.art-80529df392474644866be253d9be0dc9 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T03:28:23Z |
| publishDate | 2021-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-80529df392474644866be253d9be0dc92023-11-23T09:46:50ZengMDPI AGMolecules1420-30492021-12-012624762110.3390/molecules26247621Experimental and Computational Analysis of <i>Para</i>-Hydroxy Methylcinnamate following PhotoexcitationJack Dalton0Gareth W. Richings1Jack M. Woolley2Temitope T. Abiola3Scott Habershon4Vasilios G. Stavros5Department of Chemistry, University of Warwick, Coventry CV4 7AL, UKDepartment of Chemistry, University of Warwick, Coventry CV4 7AL, UKDepartment of Chemistry, University of Warwick, Coventry CV4 7AL, UKDepartment of Chemistry, University of Warwick, Coventry CV4 7AL, UKDepartment of Chemistry, University of Warwick, Coventry CV4 7AL, UKDepartment of Chemistry, University of Warwick, Coventry CV4 7AL, UK<i>Para</i>-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 S<sub>1</sub>(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 S<sub>1</sub>(ππ*) state is yet to be accurately measured. In this study, we use time-resolved ion-yield and photoelectron spectroscopies to precisely determine the S<sub>1</sub>(ππ*) lifetime for the s-<i>cis</i> conformer of <i>para</i>-hydroxy methylcinnamate, combined with time-dependent density functional theory to determine the major non-radiative decay route. We find the S<sub>1</sub>(ππ*) state lifetime of s-<i>cis para</i>-hydroxy methylcinnamate to be ∼2.5 picoseconds, and the major non-radiative decay route to follow the [<sup>1</sup>ππ*→<sup>1</sup>nπ*→<sup>3</sup>ππ*→S<sub>0</sub>] pathway. These results also concur with previous photodynamical studies on structurally similar molecules, such as <i>para</i>-coumaric acid and methylcinnamate.https://www.mdpi.com/1420-3049/26/24/7621ultrafast spectroscopyDFTgas-phaseVMIphotochemistryphotophysics |
| spellingShingle | Jack Dalton Gareth W. Richings Jack M. Woolley Temitope T. Abiola Scott Habershon Vasilios G. Stavros Experimental and Computational Analysis of <i>Para</i>-Hydroxy Methylcinnamate following Photoexcitation Molecules ultrafast spectroscopy DFT gas-phase VMI photochemistry photophysics |
| title | Experimental and Computational Analysis of <i>Para</i>-Hydroxy Methylcinnamate following Photoexcitation |
| title_full | Experimental and Computational Analysis of <i>Para</i>-Hydroxy Methylcinnamate following Photoexcitation |
| title_fullStr | Experimental and Computational Analysis of <i>Para</i>-Hydroxy Methylcinnamate following Photoexcitation |
| title_full_unstemmed | Experimental and Computational Analysis of <i>Para</i>-Hydroxy Methylcinnamate following Photoexcitation |
| title_short | Experimental and Computational Analysis of <i>Para</i>-Hydroxy Methylcinnamate following Photoexcitation |
| title_sort | experimental and computational analysis of i para i hydroxy methylcinnamate following photoexcitation |
| topic | ultrafast spectroscopy DFT gas-phase VMI photochemistry photophysics |
| url | https://www.mdpi.com/1420-3049/26/24/7621 |
| work_keys_str_mv | AT jackdalton experimentalandcomputationalanalysisofiparaihydroxymethylcinnamatefollowingphotoexcitation AT garethwrichings experimentalandcomputationalanalysisofiparaihydroxymethylcinnamatefollowingphotoexcitation AT jackmwoolley experimentalandcomputationalanalysisofiparaihydroxymethylcinnamatefollowingphotoexcitation AT temitopetabiola experimentalandcomputationalanalysisofiparaihydroxymethylcinnamatefollowingphotoexcitation AT scotthabershon experimentalandcomputationalanalysisofiparaihydroxymethylcinnamatefollowingphotoexcitation AT vasiliosgstavros experimentalandcomputationalanalysisofiparaihydroxymethylcinnamatefollowingphotoexcitation |