Low-lying electronic excitations and optical absorption spectra of the black dye sensitizer: a first-principles study |
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Authors: | Email author" target="_blank">Alain?DelgadoEmail author Stefano?Corni Guido?Goldoni |
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Institution: | 1.CNR-NANO S3, Institute for Nanoscience,Modena,Italy;2.Centro de Aplicaciones Tecnológicas y Desarrollo Nuclear,La Habana,Cuba;3.CNR-NANO S3, Institute for Nanoscience and Physics Department,University of Modena and Reggio Emilia,Modena,Italy |
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Abstract: | We report on ab-initio calculations of the electronic structure and optical absorption response of the black dye sensitizer
in gas phase. We show that, despite the large size of this molecule, the second-order multiconfiguration quasi-degenerate
perturbation theory (MC-QDPT) can be used to calculate vertical excitation energies, oscillator strengths and optical absorption
spectra. The zeroth-order reference states entering perturbation calculations are complete active space (CAS) configuration
interaction (CI) wave functions computed for 12 active electrons distributed in 12 active orbitals. We found that the CI approach
is not enough for taking into account the strong dynamical correlation effects in this system. In fact, the excitation energies
of the CAS-CI target states are strongly renormalized by the MC-QDPT calculations. In the calculated absorption spectra, the
analysis of the perturbed wavefunctions revealed that the stronger absorption bands correspond to metal-to-ligand and ligand-to-ligand
charge transfer processes. Comparison with independent time-dependent extension (TDDFT) calculations performed with different
functionals shows that corrections to the long-range behavior of the functional is pivotal to achieve agreement with the MC-QDPT
results. |
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