Critical Assessment of Density Functional Theory in Computing Linear and Nonlinear Optical Properties of Organic Molecules
Wednesday 25. August in room M1.05 at 14:00.
Dr. Robert Zalesny
Theoretical Chemistry Group
Institute of Physical and Theoretical Chemistry
Wroclaw University of Technology, Wroclaw, Poland
Despite undisputed success of density functional theory (DFT) in various branches of chemistry and physics, an application of the DFT for reliable prediction of nonlinear optical properties of molecules has been questioned over a decade ago. As it was shown by Champagne and coworkers, most of the traditional DFT schemes were unable to qualitatively predict the response of conjugated oligomers to static electric field. Long-range corrected (LRC) functionals, like LC-BLYP and CAM-B3LYP, were proposed to alleviate this deficiency. The reliability of predictions of linear (intramolecular charge-
transfer excitations) and nonlinear optical properties (molecular hyperpolarizabilities) by LRC schemes will be discussed for various groups of organic systems (azobenzenes, organofullerenes, etc.) with an eye towards computing vibrational corrections to hyperpolarizabilities using DFT.
