Dynamics of Excited States of the Carotenoid Peridinin in Polar Solvents: Dependence on Excitation Wavelength, Viscosity, and Temperature.
(2003) In The Journal of Physical Chemistry Part B 107(22). p.5339-5348- Abstract
- The dynamics of the excited states of the carotenoid peridinin in polar solvents were studied using femtosecond transient absorption spectroscopy in the spectral range of 500-1900 nm. A broadening of the absorption spectrum in polar solvents is caused by a distribution of conformers having different ground-state properties. In addition, the dependence of the peridinin lifetime on the excitation wavelength reveals that two peridinin forms coexist in protic solvents, where a "red"-absorbing form is produced by hydrogen bonding via the carbonyl group. The observed dynamics show that the S1 and intramolecular charge transfer (ICT) states of peridinin are strongly coupled, forming a collective S1/ICT state whose lifetime is determined by the... (More)
- The dynamics of the excited states of the carotenoid peridinin in polar solvents were studied using femtosecond transient absorption spectroscopy in the spectral range of 500-1900 nm. A broadening of the absorption spectrum in polar solvents is caused by a distribution of conformers having different ground-state properties. In addition, the dependence of the peridinin lifetime on the excitation wavelength reveals that two peridinin forms coexist in protic solvents, where a "red"-absorbing form is produced by hydrogen bonding via the carbonyl group. The observed dynamics show that the S1 and intramolecular charge transfer (ICT) states of peridinin are strongly coupled, forming a collective S1/ICT state whose lifetime is determined by the degree of ICT character. In nonpolar solvent, pure S1 character with a lifetime of ~160 ps is observed, whereas in polar solvents an increase in the ICT character leads to a lifetime as short as 10 ps in methanol and 13 ps in ethylene glycol. In protic solvents, the ICT character of the S1/ICT state of the red peridinin form is further enhanced by hydrogen bonding, resulting in lifetimes shorter than 6 ps. A weak dependence of peridinin dynamics on viscosity shows that the ICT state is not formed via a twisted ICT mechanism. At 190 K in methanol, a significant increase in the S1/ICT lifetime is observed, suggesting that thermal coupling is involved in the S1/ICT state mixing. At 77 K in ethylene glycol glass, a multiexponential decay is revealed, indicating the presence of several conformers with different S1/ICT state properties. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/128243
- author
- Zigmantas, Donatas LU ; Hiller, R G ; Yartsev, Arkady LU ; Sundström, Villy LU and Polivka, Tomas LU
- organization
- publishing date
- 2003
- type
- Contribution to journal
- publication status
- published
- subject
- in
- The Journal of Physical Chemistry Part B
- volume
- 107
- issue
- 22
- pages
- 5339 - 5348
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000183223500032
- scopus:0038171507
- ISSN
- 1520-5207
- DOI
- 10.1021/jp0272318
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
- id
- 21b8efa2-7a97-4a26-95b8-c943f0183490 (old id 128243)
- date added to LUP
- 2016-04-01 17:06:31
- date last changed
- 2022-03-22 23:23:06
@article{21b8efa2-7a97-4a26-95b8-c943f0183490, abstract = {{The dynamics of the excited states of the carotenoid peridinin in polar solvents were studied using femtosecond transient absorption spectroscopy in the spectral range of 500-1900 nm. A broadening of the absorption spectrum in polar solvents is caused by a distribution of conformers having different ground-state properties. In addition, the dependence of the peridinin lifetime on the excitation wavelength reveals that two peridinin forms coexist in protic solvents, where a "red"-absorbing form is produced by hydrogen bonding via the carbonyl group. The observed dynamics show that the S1 and intramolecular charge transfer (ICT) states of peridinin are strongly coupled, forming a collective S1/ICT state whose lifetime is determined by the degree of ICT character. In nonpolar solvent, pure S1 character with a lifetime of ~160 ps is observed, whereas in polar solvents an increase in the ICT character leads to a lifetime as short as 10 ps in methanol and 13 ps in ethylene glycol. In protic solvents, the ICT character of the S1/ICT state of the red peridinin form is further enhanced by hydrogen bonding, resulting in lifetimes shorter than 6 ps. A weak dependence of peridinin dynamics on viscosity shows that the ICT state is not formed via a twisted ICT mechanism. At 190 K in methanol, a significant increase in the S1/ICT lifetime is observed, suggesting that thermal coupling is involved in the S1/ICT state mixing. At 77 K in ethylene glycol glass, a multiexponential decay is revealed, indicating the presence of several conformers with different S1/ICT state properties.}}, author = {{Zigmantas, Donatas and Hiller, R G and Yartsev, Arkady and Sundström, Villy and Polivka, Tomas}}, issn = {{1520-5207}}, language = {{eng}}, number = {{22}}, pages = {{5339--5348}}, publisher = {{The American Chemical Society (ACS)}}, series = {{The Journal of Physical Chemistry Part B}}, title = {{Dynamics of Excited States of the Carotenoid Peridinin in Polar Solvents: Dependence on Excitation Wavelength, Viscosity, and Temperature.}}, url = {{http://dx.doi.org/10.1021/jp0272318}}, doi = {{10.1021/jp0272318}}, volume = {{107}}, year = {{2003}}, }