Energetics and Dynamics of the Low-Lying Electronic States of Constrained Polyenes: Implications for Infinite Polyenes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60076658%3A12310%2F13%3A43885279" target="_blank" >RIV/60076658:12310/13:43885279 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/jp310592s" target="_blank" >http://dx.doi.org/10.1021/jp310592s</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jp310592s" target="_blank" >10.1021/jp310592s</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Energetics and Dynamics of the Low-Lying Electronic States of Constrained Polyenes: Implications for Infinite Polyenes

Popis výsledku v původním jazyce

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

Název v anglickém jazyce

Energetics and Dynamics of the Low-Lying Electronic States of Constrained Polyenes: Implications for Infinite Polyenes

Popis výsledku anglicky

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

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

BO - Biofyzika

OECD FORD obor

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Projekt

<a href="/cs/project/ME09037" target="_blank" >ME09037: Excitované stavy karbonylových karotenoidů a jejich role ve fotochemických reakcích</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2013

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Svazek periodika

117

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

17

Strana od-do

1449-1465

Kód UT WoS článku

000315432300009

EID výsledku v databázi Scopus

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