We analyze potentials and limits of the Time- Dependent Density Functional Theory (TD-DFT) approach for the determination of excited-state geometries of organic molecules in gas-phase and in solution. Three very popular DFT exchange- correlation functionals, two hybrids (B3LYP and PBE0) and one long-range corrected (CAM-B3LYP), are here investigated, and the results are compared to the correlated RI-CC2 wave function approach. Solvent effects are further analyzed by means of a polarizable continuum model. A total of 15 organic chromophores (including both small molecules and larger push−pull systems) are considered as prototypes of n → π* and π → π* singlet excitations. Our analysis allows to point out specific correlations between the accuracy of the various functionals and the type of excitation and/or the type of chemical bonds involved. We find that while the best ground-state geometries are obtained with PBE0 and B3LYP, CAM- B3LYP yields the most accurate description of electronic and geometrical characteristics of excited states, both in gas-phase and in solution.
|Autori interni:||GUIDO, Ciro Achille|
|Autori:||Ciro A. Guido;Stefan Knecht;Jacob Kongsted;Benedetta Mennucci|
|Titolo:||Benchmarking Time-Dependent Density Functional Theory for Excited State Geometries of Organic Molecules in Gas-Phase and in Solution|
|Anno del prodotto:||2013|
|Digital Object Identifier (DOI):||10.1021/ct400021c|
|Appare nelle tipologie:||1.1 Articolo in rivista|