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Journal Article

Electronically Excited States of Higher Acenes up to Nonacene: A Density Functional Theory/Multireference Configuration Interaction Study


Doerr,  Markus
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;


Sanchez-Garcia,  Elsa
Research Group Sánchez-García, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Bettinger, H. F., Tönshoff, C., Doerr, M., & Sanchez-Garcia, E. (2016). Electronically Excited States of Higher Acenes up to Nonacene: A Density Functional Theory/Multireference Configuration Interaction Study. Journal of Chemical Theory and Computation, 12(1), 305-312. doi:10.1021/acs.jctc.5b00671.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0029-6447-E
While the optical spectra of the acene series up to pentacene provide textbook examples for the annulation principle, the spectra of the larger members are much less understood. The present work provides an investigation of the optically allowed excited states of the acene series from pentacene to nonacene, the largest acene observed experimentally, using the density functional based multireference configuration method (DFT/MRCI). For this purpose, the ten lowest energy states of the B2u and B3u irreducible representations were computed. In agreement with previous computational investigations, the electronic wave functions of the acenes acquire significant multireference character with increasing acene size. The HOMO → LUMO excitation is the major contributor to the 1La state (p band, B2u) also for the larger acenes. The oscillator strength decreases with increasing length. The 1Lb state (α band, B3u), so far difficult to assign for the larger acenes due to overlap with photoprecursor bands, becomes almost insensitive to acene length. The 1Bb state (β band, B3u) also moves only moderately to lower energy with increasing acene size. Excited states of B3u symmetry that formally result from double excitations involving HOMO, HOMO–1, LUMO, and LUMO+1 decrease in energy much faster with system size. One of them (D1) has very small oscillator strength but becomes almost isoenergetic with the 1La state for nonacene. The other (D2) also has low oscillator strength as long as it is higher in energy than 1Bb. Once it is lower in energy than the 1Bb state, both states interact strongly resulting in two states with large oscillator strengths. The emergence of two strongly absorbing states is in agreement with experimental observations. The DFT/MRCI computations reproduce experimental excitation energies very well for pentacene and hexacene (within 0.1 eV). For the larger acenes deviations are larger (up to 0.2 eV), but qualitative agreement is observed.