Energetics and Dynamics of the Low-Lying Electronic States of Constrained Polyenes: Implications for Infinite Polyenes
Result description
Steady-state and ultrafast transient absorption spectra were obtained for a series of conformationally constrained, isomerically pure polyenes with 5-23 conjugated double bonds (N). These data and fluorescence spectra of the shorter polyenes reveal the Ndependence of the energies of six B-1(u)+ and two (1)A(g)(-) excited states. The B-1(u)+ states converge to a common infinite polyene limit of 15 900 +/- 100 cm(-1). The two excited (1)A(g)(-) states, however, exhibit a large (similar to 9000 cm-1) energy difference in the infinite polyene limit, in contrast to the common value previously predicted by theory. EOM-CCSD ab initio and MNDO-PSDCI semiempirical MO theories account for the experimental transition energies and intensities. The complex, multistep dynamics of the 1(1)B(u)(+) -} 2(1)A(g)(-) -} 1(1)A(g)(-) excited state decay pathways as a function of N are compared with kinetic data from several natural and synthetic carotenoids. Distinctive transient absorption signals in the v
Keywords
open-chain carotenoidsmolecular-orbital theorylight-harvesting functionconjugation length dependenceresolved absorption-spectroscopytrans-beta-caroteneexcited singlet-stateresolution optical spectroscopy
The result's identifiers
Result code in IS VaVaI
Result on the web
DOI - Digital Object Identifier
Alternative languages
Result language
angličtina
Original language name
Energetics and Dynamics of the Low-Lying Electronic States of Constrained Polyenes: Implications for Infinite Polyenes
Original language description
Steady-state and ultrafast transient absorption spectra were obtained for a series of conformationally constrained, isomerically pure polyenes with 5-23 conjugated double bonds (N). These data and fluorescence spectra of the shorter polyenes reveal the Ndependence of the energies of six B-1(u)+ and two (1)A(g)(-) excited states. The B-1(u)+ states converge to a common infinite polyene limit of 15 900 +/- 100 cm(-1). The two excited (1)A(g)(-) states, however, exhibit a large (similar to 9000 cm-1) energy difference in the infinite polyene limit, in contrast to the common value previously predicted by theory. EOM-CCSD ab initio and MNDO-PSDCI semiempirical MO theories account for the experimental transition energies and intensities. The complex, multistep dynamics of the 1(1)B(u)(+) -} 2(1)A(g)(-) -} 1(1)A(g)(-) excited state decay pathways as a function of N are compared with kinetic data from several natural and synthetic carotenoids. Distinctive transient absorption signals in the v
Czech name
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Czech description
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Classification
Type
Jx - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
BO - Biophysics
OECD FORD branch
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Result continuities
Project
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2013
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Physical Chemistry A
ISSN
1089-5639
e-ISSN
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Volume of the periodical
117
Issue of the periodical within the volume
7
Country of publishing house
US - UNITED STATES
Number of pages
17
Pages from-to
1449-1465
UT code for WoS article
000315432300009
EID of the result in the Scopus database
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Basic information
Result type
Jx - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP
BO - Biophysics
Year of implementation
2013