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Exciton coherence lifetimes from electronic structure
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Image of FIG. 1.
FIG. 1.

Excitonic dimers considered in this study, from left-to-right [2,2’] dithia-anthracenophane (DTA), 3,5-bis(anthracen-2-yl)-tert-butylbenzene (MDAB), and 1,2-bis-(anthracen-9-yl)benzene (ODAB).

Image of FIG. 2.
FIG. 2.

An example of the bath correlation functions for ODAB, produced from the approximations discussed in the text. C mn (ω) is constructed for every pair of states below 6.5 eV within the IMDHO model, and used to construct the Redfield tensor.

Image of FIG. 3.
FIG. 3.

An example of how the [2,2’] dithia-anthracenophane (DTA) state populations evolve under the application of an 80 fs oscillating electric field of 0.05 a.u. along one of three axes (denoted by the red arrow in the figure). On the right, the corresponding stick spectra are shown, with and without reorganization energy, and in blue the envelope of the exciting pulse.

Image of FIG. 4.
FIG. 4.

Energies of adiabatic, and quasidiabatic transfer states as a function of dimensionless displacement along [2,2’] dithia-anthracenophane's 19th (left), and 37th (right) normal mode. In the figure on the left it is immediately clear by inspection that the diabatic states are more harmonic than the adiabatic states. The figure on the right is an example where the accuracy of using Eq. (10) is questionable.

Image of FIG. 5.
FIG. 5.

(The polarization anisotropy decay of ODAB calculated in this work (ωB97//6-31g**) and compared to the analytically fit experimental decay of Yamazaki. Below, the evolution of the coherence between bright adiabatic states, 3 and 4 (ρ34(t) + ρ43(t)). The decay of the coherence between these two states is much faster than the decay of the observable.


Generic image for table
Table I.

Singlet excited state energies (eV) and oscillator strengths, f, produced by RI-CIS(D0)//cc-pvdz follow the same trends as the B3LYP results, although the values of the couplings are more poorly reproduced.

Generic image for table
Table II.

State couplings β(cm−1) as estimated from half the difference of bright excited state energies in the cc-pvdz basis for various methods differing in their treatment of exchange and correlation. The agreement is best with the addition of long-range correlation (last column). The addition of exchange appears to worsen the results. Basis set dependence is addressed below.

Generic image for table
Table III.

State couplings β(cm−1) as estimated from half the difference of bright excited state energies in the QZVP basis. With this basis these quantities are nearly converged with respect to basis-set size, but TDDFT is still unable to reproduce the qualitative trend.

Generic image for table
Table IV.

Pure-dephasing time (ps) between the two brightest states (), as obtained from two different choices of electronic basis, compared to the experimental .


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Exciton coherence lifetimes from electronic structure