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  • Wiley  (40)
  • American Institute of Physics (AIP)  (32)
  • American Chemical Society (ACS)  (8)
  • 11
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 4783-4789 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Vibrationally resolved fluorescence and fluorescence excitation spectra have been measured for solid solutions of 2,2'-bithiophene, 2,2'-thienylpyrrole, and 2,2'-bipyrrole in n-hexane at 4.2 K. The vibronic development of the spectra of all three molecules is very similar to what has been reported previously for longer polythiophene oligomers. Bithiophene and thienylpyrrole have similar S0 to S1 excitation energies: 29 603 and 30 006 cm−1, respectively. The S0 to S1 excitation energy of bipyrrole is significantly higher, 32 720 cm−1, indicating nonplanarity of the pyrrole rings. The vibrational development of the spectra and coincident origin energies in excitation and emission establish that the S0 to S1 transition is symmetry allowed for all three molecules, reasonably described in simple molecular orbital theory as the promotion of one electron from the highest energy occupied molecular orbital (HOMO) to the lowest energy unoccupied molecular orbital (LUMO).
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  • 12
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 6367-6376 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In a previous letter [J. Chem. Phys. 92, 4622 (1990)] we reported the first observation of the 2 1Ag state of cis-hexatriene in a supersonic jet expansion by using resonance enhanced multiphoton ionization spectroscopy. Here, the vibrational analysis of the 1 1Ag→2 1Ag excitation spectrum of cis-hexatriene is presented. The excitation spectrum shows that cis-hexatriene in the 2 1Ag state deviates slightly from planarity; a conclusion which is corroborated by ab initio calculations indicating that the nonplanarity primarily involves the terminal hydrogen atoms. Except for observable intensity in the low frequency modes associated with the small out of plane distortion, the vibronic development of the 1 1Ag→2 1Ag transition in cis-hexatriene is similar to that observed for other polyenes: the 0–0 transition is the most intense feature and the next most intense band is the C(large-closed-square)C stretching fundamental. Thus the general features of the electronic structure of the cis-hexatriene 2 1Ag state are analogous to those of other polyenes.
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  • 13
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 1684-1691 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Fluorescence and fluorescence excitation spectra for low temperature n-alkane solutions of α,ω-dithenylpolyenes with two, three, and four polyene double bonds have been measured. The fundamental frequencies in the vibronic development of the fully resolved spectra are either nearly identical to modes seen for unsubstituted polyenes or nearly identical to modes seen for polythiophene oligomers. The degree to which thiophene ring modes contribute to the spectra decreases with increasing polyene chain length. In the tetraene, the 2 1Ag state is 2760 cm−1 lower in energy than the 1 1Bu state, in the triene it is 1570 cm−1 lower, and in the diene these two states are nearly degenerate. The 2 1Ag and 1 1Bu excitation energies are well fit by a simple theoretical model which also gives a description of the π-electron distributions in the 1 1Ag, 2 1Ag, and 1 1Bu states.
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  • 14
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 5838-5842 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A simple model based on Huckel theory for interpreting linear polyene electronic structure is presented. The essential ingredients are the use of alternating resonance integrals to obtain the proper chain-length dependence of the 1 1Bu highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) excitation energy and mixing of the HOMO to LUMO+1 and HOMO to LUMO double-excitation configurations to properly describe the 2 1Ag state. With the proper choice of parameters, this model reproduces all 25 2 1Ag and 1 1Bu 0–0 excitation energies that have thus far been measured for linear polyenes in low-temperature hydrocarbon solutions.
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  • 15
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 5422-5428 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High resolution fluorescence and fluorescence excitation spectra have been obtained for the all-trans polyene 2,4,6,8,10,12,14,16-octadecaoctaene in an n-hexadecane matrix at 4.2 K. This is the longest discrete linear polyene for which such data are known. The 1 1Ag to 2 1Ag 0–0 band at 17 871 cm−1 is 4900 cm−1 below 1 1Ag to 1 1Bu 0–0 band at 22 770 cm−1. Both of these excitation energies are approximately what would have been predicted by fitting the 0–0 excitation energies of shorter polyenes with N double bonds by a 1/N curve and extrapolating to N=8. These spectra provide further information on the vibronic levels of the ground (1 1Ag) and first excited (2 1Ag ) singlet states and provide insight into the structure of the conjugated polymer polyacetylene. As has been found in the case of shorter polyenes, the strongest vibronic feature (assigned as a totally symmetric C=C stretch) increases 1554 cm−1 in the 1 1Ag state to 1799 cm−1 in the 2 1Ag state) also for the octaene. Possible reasons for this increase are discussed.
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  • 16
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 2492-2495 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The 0–0 excitation energy of a 1Ag state of 2,2'-bithiophene has been determined by measuring the two-photon fluorescence excitation spectrum of a dilute solution of this molecule in crystalline n-hexane at 77 K. Because the 0–0 energy is what would have been predicted by extrapolating previously measured α,ω-dithienylpolyene 2 1Ag 0–0 energies to zero polyene chain length, it is assigned to the 2 1Ag state. The 0–0 band is centered at 36 173 cm−1, approximately 6570 cm−1 above the 0–0 of the 1 1Ag to 1 1Bu transition. This order of bithiophene excited singlet states is opposite to that of the linear polyene with the same number of double bond but may reverse for chains longer than six repeat units.
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  • 17
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 7875-7875 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
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  • 18
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 165-169 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Fluorescence and fluorescence excitation spectra have been measured for solid solutions of tetrathiophene in tetradecane at 12 and 4.2 K. At 4.2 K, the spectra exhibit full vibrational resolution {inhomogeneous origin [full width at half-maximum, (FWHM)] approximately 5 cm−1 }. Narrow band excitation and detection establish that there are four independent, but nearly identical excitation/emission pairs with dipole allowed origins at 22 248, 22 241, 22 214, and 22 187 cm−1. The data are consistent with the idea that these multiple spectra come from a single tetrathiophene confomer which can occupy four different sites in the tetradecane lattice. The vibrational frequencies of the modes in the ground (excited) state that couple strongly to the electronic excitation are 162, 327, 703, 1478, and 1531 cm−1 (161, 333, 688, 1235, and 1551 cm−1 ). The overlap of the excitation and emission origins and vibrational development of the spectra establish that the S0 to S1 transition is symmetry allowed (1 1Ag to 1 1Bu for C2h all-trans tetrathiophene) with the excited 1 1Bu state described reasonably as being derived from the ground state by the promotion of one electron from the highest energy occupied molecular orbital to the lowest energy unoccupied molecular orbital (HOMO to LUMO).
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  • 19
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 399-407 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Vibrationally resolved 1 1Ag→2 1Ag excitation spectra and decay times for cis,trans-1,3,5,7-octatetraene seeded in a supersonic He expansion have been measured by two-color resonance enhanced two-photon ionization spectroscopy. The excitation energy of the 1 1Ag→2 1Ag 0–0 band (29 035 cm−1 ) is ∼6500 cm−1 lower than the 35 484 cm−1 excitation energy of the 1 1Ag→1 1Bu 0–0 band. The intensity pattern of the vibronic development of this spectrum is qualitatively similar to the pattern observed previously in solid state experiments. However, a detailed analysis of the vibrational structure reveals that the electronic structure of the 2 1Ag state is more susceptible to external perturbation than previously suspected. The decay times measured for vibronic levels in the 2 1Ag state decrease with increasing vibrational energy, most dramatically for vibrational energies 1200 cm−1 and higher. This indicates the increasing importance of a nonradiative decay channel which is most reasonably associated, at least in part, with cis-trans isomerization in the 2 1Ag state.
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  • 20
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 908-917 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Vibrationally resolved optical spectra, fluorescence decay times, and fluorescence quantum yields have been measured for all-trans diphenyloctatetraene and all-trans diphenyloctatetraene substituted in the para position(s) of the phenyl ring(s) with an electron donor (MeO) or (and) and electron acceptor (CN). The electronic excitation energies, S0–S1 and S0–S2 transition dipoles and vibrational properties of the spectra provide a detailed picture of the effects of donor–acceptor substitution on the S0, S1, and S2 states. The electronic excitation energies are well fit by a simple parametrized quantum-mechanical model for polyene electronic structure which is used to estimate substituent-induced shifts in π-electron density in the S0, S1, and S2 states.
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