First-Principles Simulation of Absorption Bands of Fluorenone in Zeolite L

The absorption spectrum of fluorenone in zeolite L is calculated from first-principles simulations. The broadening of each band is obtained from the explicit treatment of the interactions between the chromophore and its environment in the statistical ensemble. The comparison between the simulated and measured spectra reveals the main factors affecting the spectrum of the chromophore in hydrated zeolite L. Whereas each distinguishable band is found to originate from a single electronic transition, the bandwidth is determined by the statistical nature of the environment of the fluorenone molecule. The K + ...O=C motif is retained in all conformations. Although the interactions between K + and the fluorenone carbonyl group result in an average lengthening of the C=O bond and in a redshift of the lowest energy absorption band compared to gas phase or non-polar solvents, the magnitude of this shift is noticeably smaller than the total shift. An important factor affecting the shape of the band is fluorenone’s orientation, which is strongly affected by the presence of water. The effect of direct interactions between fluorenone and water is, however, negligible.