Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study
Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorop...
| Main Authors: | , , , , , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2015
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| Online Access: | https://hdl.handle.net/10356/103527 http://hdl.handle.net/10220/38764 |
| _version_ | 1811680414209671168 |
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| author | Zhao, Yang Bricker, William P. Shenai, Prathamesh M. Ghosh, Avishek Liu, Zhengtang Enriquez, Miriam Grace M. Lambrev, Petar H. Tan, Howe-Siang Lo, Cynthia S. Tretiak, Sergei Fernandez-Alberti, Sebastian |
| author2 | School of Materials Science & Engineering |
| author_facet | School of Materials Science & Engineering Zhao, Yang Bricker, William P. Shenai, Prathamesh M. Ghosh, Avishek Liu, Zhengtang Enriquez, Miriam Grace M. Lambrev, Petar H. Tan, Howe-Siang Lo, Cynthia S. Tretiak, Sergei Fernandez-Alberti, Sebastian |
| author_sort | Zhao, Yang |
| collection | NTU |
| description | Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. Modeling this process with non-adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales. Even given smaller electron-vibrational couplings compared to common organic conjugated chromophores, these molecules are able to efficiently dissipate about 1 eV of electronic energy into heat on the timescale of around 200 fs. This is achieved via selective participation of specific atomic groups and complex global migration of the wavefunction from the outer to inner ring, which may have important implications for biological light-harvesting function. |
| first_indexed | 2024-10-01T03:24:40Z |
| format | Journal Article |
| id | ntu-10356/103527 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T03:24:40Z |
| publishDate | 2015 |
| record_format | dspace |
| spelling | ntu-10356/1035272023-02-28T19:21:24Z Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study Zhao, Yang Bricker, William P. Shenai, Prathamesh M. Ghosh, Avishek Liu, Zhengtang Enriquez, Miriam Grace M. Lambrev, Petar H. Tan, Howe-Siang Lo, Cynthia S. Tretiak, Sergei Fernandez-Alberti, Sebastian School of Materials Science & Engineering School of Physical and Mathematical Sciences Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. Modeling this process with non-adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales. Even given smaller electron-vibrational couplings compared to common organic conjugated chromophores, these molecules are able to efficiently dissipate about 1 eV of electronic energy into heat on the timescale of around 200 fs. This is achieved via selective participation of specific atomic groups and complex global migration of the wavefunction from the outer to inner ring, which may have important implications for biological light-harvesting function. Published version 2015-10-01T07:20:58Z 2019-12-06T21:14:37Z 2015-10-01T07:20:58Z 2019-12-06T21:14:37Z 2015 2015 Journal Article Bricker, W. P., Shenai, P. M., Ghosh, A., Liu, Z., Enriquez, M. G. M., Lambrev, P. H., et al. (2015). Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study. Scientific Reports, 5, 13625-. 2045-2322 https://hdl.handle.net/10356/103527 http://hdl.handle.net/10220/38764 10.1038/srep13625 26346438 en Scientific Reports This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ application/pdf |
| spellingShingle | Zhao, Yang Bricker, William P. Shenai, Prathamesh M. Ghosh, Avishek Liu, Zhengtang Enriquez, Miriam Grace M. Lambrev, Petar H. Tan, Howe-Siang Lo, Cynthia S. Tretiak, Sergei Fernandez-Alberti, Sebastian Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study |
| title | Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study |
| title_full | Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study |
| title_fullStr | Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study |
| title_full_unstemmed | Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study |
| title_short | Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study |
| title_sort | non radiative relaxation of photoexcited chlorophylls theoretical and experimental study |
| url | https://hdl.handle.net/10356/103527 http://hdl.handle.net/10220/38764 |
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