Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study

William P. Bricker, Prathamesh M. Shenai, Avishek Ghosh, Zhengtang Liu, Miriam Grace M. Enriquez, Petar H. Lambrev, Howe Siang Tan, Cynthia S. Lo, Sergei Tretiak, Sebastian Fernandez-Alberti, Yang Zhao

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25 Citations (Scopus)

Abstract

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.

Original languageEnglish
Article number13625
JournalScientific reports
Volume5
DOIs
Publication statusPublished - Sep 8 2015

ASJC Scopus subject areas

  • General

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    Bricker, W. P., Shenai, P. M., Ghosh, A., Liu, Z., Enriquez, M. G. M., Lambrev, P. H., Tan, H. S., Lo, C. S., Tretiak, S., Fernandez-Alberti, S., & Zhao, Y. (2015). Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study. Scientific reports, 5, [13625]. https://doi.org/10.1038/srep13625