An Additive Long-range Potential to Correct for the Charge-transfer Failure of Time-dependent Density Functional Theory

Andreas Dreuw, Jürgen Plötner, Michael Wormit, Martin Head-Gordon,  and Anthony Dean Dutoi 1 , 1
  • 1  Ruprecht Karls-University Heidelberg, Institute of Physical and Theoretical Chemistry,, Heidelberg, Deutschland


Time-dependent density functional theory is one of the most widely used methods for the calculation of excited states of large molecules. However, it exhibits substantial problems with charge-transfer excited states when conventional exchange-correlation functionals are employed. Here, we introduce an additive long-range potential that can, in principle, be directly employed with any existing local, GGA or hybrid-functional, without re-fitting of the original functionals. The additive potential shifts the excitation energies to higher values and corrects for the wrong asymptotic behavior of their potential energy surfaces with respect to charge-separating coordinates. First examples of its successful application are shown.

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Founded in 1887, the Zeitschrift für Physikalische Chemie covers the main developments in physical chemistry, placing with an emphasis on experimental research. It represents a combination ofdiscusses reaction kinetics and spectroscopy, surface research and electrochemistry, thermodynamics and the structure analysis of matter in its various conditions, among other topics.