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Published Online: 11 April 2002
Accepted: November 2001

Chiroptical properties from time-dependent density functional theory. I. Circular dichroism spectra of organic molecules

J. Chem. Phys. 116, 6930 (2002); https://doi.org/10.1063/1.1436466
Jochen Autschbach and Tom Ziegler
  • Department of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada
    • Stan J. A. van Gisbergen
  • Scientific Computing and Modeling and Theoretical Chemistry, FEW, Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
    • Evert Jan Baerends
  • Theoretical Chemistry, FEW, Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
    • more...
    ABSTRACT
    We report the implementation of the computation of rotatory strengths, based on time-dependent density functional theory, within the Amsterdam Density Functional program. The code is applied to the simulation of circular dichroism spectra of small and moderately sized organic molecules, such as oxiranes, aziridines, cyclohexanone derivatives, and helicenes. Results agree favorably with experimental data, and with theoretical results for molecules that have been previously investigated by other authors. The efficient algorithms allow for the simulation of CD spectra of rather large molecules at a reasonable accuracy based on first-principles theory. The choice of the Kohn–Sham potential is a critical issue. It is found that standard gradient corrected functionals often yield the correct shape of the spectrum, but the computed excitation energies are systematically underestimated for the samples being studied. The recently developed exchange-correlation potentials “GRAC” and “SAOP” often yield much better agreement here with experiments for the excitation energies. The rotatory strengths of individual transitions are usually improved by these potentials as well.

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