The excited state mixing effect is taken into account considering the difference spectra of dimers. Both the degenerate (homo) dimer as well as the nondegenerate (hetero) dimer are considered. Due to the higher excited state mixing with the two-exciton states in the homodimer, the excited state absorption (or the difference spectrum) can be strongly affected in comparison with the results obtained in the Heitler–London approximation. The difference spectrum of the heterodimer is influenced by two resonance effects (i) mixing of the ground state optical transitions of both monomers in the dimer and (ii) mixing of the excited state absorption of the excited monomer with the ground state optical transition in the nonexcited monomer. These effects have been tested by simulating the difference absorption spectra of the light-harvesting complex of photosystem II (LHC II) experimentally obtained with the 60 fs excitation pulses at zero delay times and various excitation wavelengths. The pairs of coupled chlorophylls a and b for simulations have been taken from the best LHC II assignment model obtained by simulating the steady-state spectra and the transient absorption at various excitation wavelengths. Qualitatively the spectral peculiarities of the difference spectra are explained by means of the resonance interpigment interactions, which are responsible for the excited state mixing.
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15 August 1999
Research Article|
August 15 1999
Effects of excited state mixing on transient absorption spectra in dimers: Application to photosynthetic light-harvesting complex II
Leonas Valkunas;
Leonas Valkunas
Institute of Physics, A, Gostauto 12, Vilnius 2600, Lithuania
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Vilmantas Cervinskas;
Vilmantas Cervinskas
Institute of Physics, A, Gostauto 12, Vilnius 2600, Lithuania
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Gediminas Trinkunas;
Gediminas Trinkunas
Institute of Physics, A, Gostauto 12, Vilnius 2600, Lithuania
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Marc G. Müller;
Marc G. Müller
Max-Planck-Institut fur Strahlenchemie, Muelheim a. d. Ruhr, D-45470, Germany
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Alfred R. Holzwarth
Alfred R. Holzwarth
Max-Planck-Institut fur Strahlenchemie, Muelheim a. d. Ruhr, D-45470, Germany
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J. Chem. Phys. 111, 3121–3132 (1999)
Article history
Received:
January 15 1999
Accepted:
May 11 1999
Citation
Leonas Valkunas, Vilmantas Cervinskas, Gediminas Trinkunas, Marc G. Müller, Alfred R. Holzwarth; Effects of excited state mixing on transient absorption spectra in dimers: Application to photosynthetic light-harvesting complex II. J. Chem. Phys. 15 August 1999; 111 (7): 3121–3132. https://doi.org/10.1063/1.479593
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