Time-dependent density functional theory investigation of the absorption, fluorescence, and phosphorescence spectra of solvated coumarins

Jacquemin, Denis; Perpète, Eric A.; Scalmani, Giovanni; Frisch, Michael J.; Assfeld, Xavier; Ciofini, Ilaria; Adamo, Carlo

doi:doi:10.1063/1.2361290

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The nonadiabatic deactivation paths of pyrrole

Multireference configuration interaction (MRCI) calculations have been performed for pyrrole with the aim of providing an explanation for the experimentally observed photochemical deactivation processes. Potential energy curves and minima on the crossing seam were determined using the analytic MRCI gradient and nonadiabatic coupling features of the COLUMBUS program system. A new deactivation mechanism based on an out-of-plane ring deformation is presented. This mechanism directly couples the ch...

Testing ion-neutral interaction potentials using calculated ion transport coefficients

Several commonly measured ion transport coefficients were investigated in order to determine their sensitivity for testing and comparing proposed ion-neutral interaction potentials. A variety of positive ions, negative ions, neutrals, and temperatures were included in order to draw as general a conclusion as possible. All transport coefficients considered were found to be sufficiently sensitive to be used to clearly distinguish between less and more accurate interaction potentials. It was also ...

Using time-dependent density functional theory (TD-DFT) and the polarizable continuum model, we have computed the electronic transitions of a large panel of coumarin dyes in their enol, keto, cationic, and anionic forms. Several processes have been studied: absorption, fluorescence, 0-0 phosphorescence, and triplet-triplet excitations. For each process, detailed comparison with experimental data has been carried out. Using the PBE0/6-31+G(d) scheme, it turns out that for a given electronic transition the experimental shifts resulting from the substitution of the coumarin core are nicely reproduced. Indeed, once a simple statistical correction is applied, the mean absolute errors on the absorption and fluorescence wavelengths are limited to 8 nm (0.09 eV) and 9 nm (0.07 eV), respectively. A valuable correlation between the experimental and theoretical phosphorescence auxochromic displacements has also been unravelled. The differences between the wavelengths of the various electronic processes of a given dye tend to be fairly predicted, especially for the fluorescence-phosphoresence shifts that are strongly overestimated by TD-DFT.

Article Outline

INTRODUCTION
METHODOLOGY
1. Absorption
2. Fluorescence
3. Triplet-related phenomena
RESULTS
1. Methodological study
2. Absorption
3. Fluorescence
4. Phosphorescence and triplet-triplet transitions
CONCLUSIONS

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KEYWORDS and PACS

Keywords

dyes, density functional theory, fluorescence, phosphorescence, triplet state

PACS

31.15.E-

Density-functional theory
33.50.Dq

Fluorescence and phosphorescence spectra

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http://link.aip.org/link/doi/10.1063/1.2361290

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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