Energies of low-lying excited states of linear polyenes

Ronald L. Christensen, Mary Grace I. Galinato, Emily F. Chu, Jason N. Howard, Richard D. Broene, Harry A. Frank

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

Room temperature absorption and emission spectra of the all-trans isomers of decatetraene, dodecapentaene, tetradecahexaene, and hexadecaheptaene have been obtained in a series of nonpolar solvents. The resolved vibronic features in the optical spectra of these model systems allow the accurate determination of S0 (11Ag-) → S2 (11Bu+) and S1 (21A g-) → S0 (11Ag -) electronic origins as a function of solvent polarizability. These data can be extrapolated to predict the transition energies in the absence of solvent perturbations. The effects of the terminal methyl substituents on the transition energies also can be estimated. Franck-Condon maxima in the absorption and emission spectra were used to estimate differences between S 0 (11Ag-) → S1 (21Ag-) and S0 (11A g-) → S2 (11Bu +) electronic origins and "vertical" transition energies. Experimental estimates of the vertical transition energies of unsubstituted, all-trans polyenes in vacuum as a function of conjugation length are compared with long-standing multireference configuration interaction (MRCI) treatments and with more recent ab initio calculations of the energies of the 2 1Ag- (S1) and 11B u+ (S2) states.

Original languageEnglish (US)
Pages (from-to)12629-12636
Number of pages8
JournalJournal of Physical Chemistry A
Volume112
Issue number49
DOIs
StatePublished - Dec 11 2008

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Polyenes
Excited states
excitation
emission spectra
Isomers
energy
absorption spectra
Vacuum
estimates
conjugation
electronics
configuration interaction
optical spectrum
isomers
perturbation
vacuum
room temperature
Temperature

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Christensen, R. L., Galinato, M. G. I., Chu, E. F., Howard, J. N., Broene, R. D., & Frank, H. A. (2008). Energies of low-lying excited states of linear polyenes. Journal of Physical Chemistry A, 112(49), 12629-12636. https://doi.org/10.1021/jp8060202
Christensen, Ronald L. ; Galinato, Mary Grace I. ; Chu, Emily F. ; Howard, Jason N. ; Broene, Richard D. ; Frank, Harry A. / Energies of low-lying excited states of linear polyenes. In: Journal of Physical Chemistry A. 2008 ; Vol. 112, No. 49. pp. 12629-12636.
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Christensen, RL, Galinato, MGI, Chu, EF, Howard, JN, Broene, RD & Frank, HA 2008, 'Energies of low-lying excited states of linear polyenes', Journal of Physical Chemistry A, vol. 112, no. 49, pp. 12629-12636. https://doi.org/10.1021/jp8060202

Energies of low-lying excited states of linear polyenes. / Christensen, Ronald L.; Galinato, Mary Grace I.; Chu, Emily F.; Howard, Jason N.; Broene, Richard D.; Frank, Harry A.

In: Journal of Physical Chemistry A, Vol. 112, No. 49, 11.12.2008, p. 12629-12636.

Research output: Contribution to journalArticle

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AB - Room temperature absorption and emission spectra of the all-trans isomers of decatetraene, dodecapentaene, tetradecahexaene, and hexadecaheptaene have been obtained in a series of nonpolar solvents. The resolved vibronic features in the optical spectra of these model systems allow the accurate determination of S0 (11Ag-) → S2 (11Bu+) and S1 (21A g-) → S0 (11Ag -) electronic origins as a function of solvent polarizability. These data can be extrapolated to predict the transition energies in the absence of solvent perturbations. The effects of the terminal methyl substituents on the transition energies also can be estimated. Franck-Condon maxima in the absorption and emission spectra were used to estimate differences between S 0 (11Ag-) → S1 (21Ag-) and S0 (11A g-) → S2 (11Bu +) electronic origins and "vertical" transition energies. Experimental estimates of the vertical transition energies of unsubstituted, all-trans polyenes in vacuum as a function of conjugation length are compared with long-standing multireference configuration interaction (MRCI) treatments and with more recent ab initio calculations of the energies of the 2 1Ag- (S1) and 11B u+ (S2) states.

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Christensen RL, Galinato MGI, Chu EF, Howard JN, Broene RD, Frank HA. Energies of low-lying excited states of linear polyenes. Journal of Physical Chemistry A. 2008 Dec 11;112(49):12629-12636. https://doi.org/10.1021/jp8060202