Cargando…
Pyrene, a Test Case for Deep-Ultraviolet Molecular Photophysics
[Image: see text] We determined the complete relaxation dynamics of pyrene in ethanol from the second bright state, employing experimental and theoretical broadband heterodyne detected transient grating and two-dimensional photon echo (2DPE) spectroscopy, using pulses with duration of 6 fs and cover...
Autores principales: | , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2019
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6774270/ https://www.ncbi.nlm.nih.gov/pubmed/31081636 http://dx.doi.org/10.1021/acs.jpclett.9b01325 |
_version_ | 1783456048562044928 |
---|---|
author | Picchiotti, Alessandra Nenov, Artur Giussani, Angelo Prokhorenko, Valentyn I. Miller, R. J. Dwayne Mukamel, Shaul Garavelli, Marco |
author_facet | Picchiotti, Alessandra Nenov, Artur Giussani, Angelo Prokhorenko, Valentyn I. Miller, R. J. Dwayne Mukamel, Shaul Garavelli, Marco |
author_sort | Picchiotti, Alessandra |
collection | PubMed |
description | [Image: see text] We determined the complete relaxation dynamics of pyrene in ethanol from the second bright state, employing experimental and theoretical broadband heterodyne detected transient grating and two-dimensional photon echo (2DPE) spectroscopy, using pulses with duration of 6 fs and covering a spectral range spanning from 250 to 300 nm. Multiple lifetimes are assigned to conical intersections through a cascade of electronic states, eventually leading to a rapid population of the lowest long-living excited state and subsequent slow vibrational cooling. The lineshapes in the 2DPE spectra indicate that the efficiency of the population transfer depends on the kinetic energy deposited into modes required to reach a sloped conical intersection, which mediates the decay to the lowest electronic state. The presented experimental–theoretical protocol paves the way for studies on deep-ultraviolet-absorbing biochromophores ubiquitous in genomic and proteic systems. |
format | Online Article Text |
id | pubmed-6774270 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-67742702019-10-03 Pyrene, a Test Case for Deep-Ultraviolet Molecular Photophysics Picchiotti, Alessandra Nenov, Artur Giussani, Angelo Prokhorenko, Valentyn I. Miller, R. J. Dwayne Mukamel, Shaul Garavelli, Marco J Phys Chem Lett [Image: see text] We determined the complete relaxation dynamics of pyrene in ethanol from the second bright state, employing experimental and theoretical broadband heterodyne detected transient grating and two-dimensional photon echo (2DPE) spectroscopy, using pulses with duration of 6 fs and covering a spectral range spanning from 250 to 300 nm. Multiple lifetimes are assigned to conical intersections through a cascade of electronic states, eventually leading to a rapid population of the lowest long-living excited state and subsequent slow vibrational cooling. The lineshapes in the 2DPE spectra indicate that the efficiency of the population transfer depends on the kinetic energy deposited into modes required to reach a sloped conical intersection, which mediates the decay to the lowest electronic state. The presented experimental–theoretical protocol paves the way for studies on deep-ultraviolet-absorbing biochromophores ubiquitous in genomic and proteic systems. American Chemical Society 2019-05-13 2019-06-20 /pmc/articles/PMC6774270/ /pubmed/31081636 http://dx.doi.org/10.1021/acs.jpclett.9b01325 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Picchiotti, Alessandra Nenov, Artur Giussani, Angelo Prokhorenko, Valentyn I. Miller, R. J. Dwayne Mukamel, Shaul Garavelli, Marco Pyrene, a Test Case for Deep-Ultraviolet Molecular Photophysics |
title | Pyrene, a Test Case for Deep-Ultraviolet Molecular
Photophysics |
title_full | Pyrene, a Test Case for Deep-Ultraviolet Molecular
Photophysics |
title_fullStr | Pyrene, a Test Case for Deep-Ultraviolet Molecular
Photophysics |
title_full_unstemmed | Pyrene, a Test Case for Deep-Ultraviolet Molecular
Photophysics |
title_short | Pyrene, a Test Case for Deep-Ultraviolet Molecular
Photophysics |
title_sort | pyrene, a test case for deep-ultraviolet molecular
photophysics |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6774270/ https://www.ncbi.nlm.nih.gov/pubmed/31081636 http://dx.doi.org/10.1021/acs.jpclett.9b01325 |
work_keys_str_mv | AT picchiottialessandra pyreneatestcasefordeepultravioletmolecularphotophysics AT nenovartur pyreneatestcasefordeepultravioletmolecularphotophysics AT giussaniangelo pyreneatestcasefordeepultravioletmolecularphotophysics AT prokhorenkovalentyni pyreneatestcasefordeepultravioletmolecularphotophysics AT millerrjdwayne pyreneatestcasefordeepultravioletmolecularphotophysics AT mukamelshaul pyreneatestcasefordeepultravioletmolecularphotophysics AT garavellimarco pyreneatestcasefordeepultravioletmolecularphotophysics |