| JANOŠ, Jiří, Dominik MADEA, Sadegh MAHVIDI, Taufiqueahmed Pirsah MUJAWAR, Jakub ŠVENDA, Jiří SUCHAN, Petr SLAVÍČEK a Petr KLÁN. Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations. Journal of Physical Chemistry. Washington, D.C.: American Chemical Society, 2020, roč. 124, č. 50, s. 10457-10471. ISSN 1089-5639. Dostupné z: https://dx.doi.org/10.1021/acs.jpca.0c08945. |
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@article{1710416,
author = {Janoš, Jiří and Madea, Dominik and Mahvidi, Sadegh and Mujawar, Taufiqueahmed Pirsah and Švenda, Jakub and Suchan, Jiří and Slavíček, Petr and Klán, Petr},
article_location = {Washington, D.C.},
article_number = {50},
doi = {http://dx.doi.org/10.1021/acs.jpca.0c08945},
keywords = {Quantum yield; Photoisomerization; Cyclization; Molecular structure; Excited states},
language = {eng},
issn = {1089-5639},
journal = {Journal of Physical Chemistry},
title = {Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations},
url = {https://doi.org/10.1021/acs.jpca.0c08945},
volume = {124},
year = {2020}
}
TY - JOUR
ID - 1710416
AU - Janoš, Jiří - Madea, Dominik - Mahvidi, Sadegh - Mujawar, Taufiqueahmed Pirsah - Švenda, Jakub - Suchan, Jiří - Slavíček, Petr - Klán, Petr
PY - 2020
TI - Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations
JF - Journal of Physical Chemistry
VL - 124
IS - 50
SP - 10457-10471
EP - 10457-10471
PB - American Chemical Society
SN - 10895639
KW - Quantum yield
KW - Photoisomerization
KW - Cyclization
KW - Molecular structure
KW - Excited states
UR - https://doi.org/10.1021/acs.jpca.0c08945
L2 - https://doi.org/10.1021/acs.jpca.0c08945
N2 - The photochemistry of bilirubin has been extensively studied due to its importance in the phototherapy of hyperbilirubinemia. In the present work, we investigated the ultrafast photodynamics of a bilirubin dipyrrinone subunit, vinylneoxanthobilirubic acid methyl ester. The photoisomerization and photocyclization reactions of its (E) and (Z) isomers were studied using femtosecond transient absorption spectroscopy and by multireference electronic structure theory, where the nonadiabatic dynamics was modeled with a Landau–Zener surface hopping technique. The following picture has emerged from the combined theoretical and experimental approach. Upon excitation, dipyrrinone undergoes a very fast vibrational relaxation, followed by an internal conversion on a picosecond time scale. The internal conversion leads either to photoisomerization or regeneration of the starting material. Further relaxation dynamics on the order of tens of picoseconds was observed in the ground state. The nonadiabatic simulations revealed a strong conformational control of the photodynamics. The ultrafast formation of a cyclic photochemical product from a less-populated conformer of the studied subunit was predicted by our calculations. We discuss the relevance of the present finding for the photochemistry of native bilirubin. The work has also pointed to the limits of semiclassical nonadiabatic simulations for simulating longer photochemical processes, probably due to the zero-point leakage issue.
ER -
JANOŠ, Jiří, Dominik MADEA, Sadegh MAHVIDI, Taufiqueahmed Pirsah MUJAWAR, Jakub ŠVENDA, Jiří SUCHAN, Petr SLAVÍČEK a Petr KLÁN. Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations. \textit{Journal of Physical Chemistry}. Washington, D.C.: American Chemical Society, 2020, roč.~124, č.~50, s.~10457-10471. ISSN~1089-5639. Dostupné z: https://dx.doi.org/10.1021/acs.jpca.0c08945.
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