Resumen
Resonance Raman and absorption spectra of 9,10-bis(2-tert-butyl-2,3- diazabicyclo[2.2.2]oct-3-yl)-anthracene (2) are measured and analyzed. The contribution of the individual vibrational normal modes to the reorganization energy is investigated. Excited-state mixed valence in this system is analyzed using density functional theory electronic structure calculations. The resonance Raman excitation profiles exhibit a resonance de-enhancement effect around 20725 cm -1, but a corresponding feature is not observed in the absorption spectrum. This unusual observation is attributed to the presence of a dipole-forbidden, vibronically allowed component of the split mixed valence excited state. The de-enhancement dip is calculated quantitatively and explained in terms of the real and imaginary components of the polarizabilities of the two overlapping excited states.
Idioma original | Inglés |
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Páginas (desde-hasta) | 5441-5447 |
Número de páginas | 7 |
Publicación | Journal of Physical Chemistry A |
Volumen | 111 |
N.º | 25 |
DOI | |
Estado | Publicada - 28 jun. 2007 |
Publicado de forma externa | Sí |