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Published Online: 24 June 2002
Accepted: March 2002

Chiroptical properties from time-dependent density functional theory. II. Optical rotations of small to medium sized organic molecules

J. Chem. Phys. 117, 581 (2002); https://doi.org/10.1063/1.1477925
Jochen Autschbach, Serguei Patchkovskii, 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 an implementation for the computation of optical rotations within the Amsterdam Density Functional program package. The code is based on time-dependent density functional response theory. Optical rotations have been calculated for a test set of 36 organic molecules with various density functionals, and employing basis sets of different quality. The results obtained in this work with nonhybrid functionals are comparable in quality to those recently reported by other authors for the B3LYP hybrid functional, but show a somewhat larger tendency to produce outlyers. The median error is approximately 20°/(dm g/cm3) for specific rotations [α]D as compared to experimental data (approximately 30% median deviation from experimental values). Thereby it is demonstrated that density functional computations can be employed to assist with the solution of stereochemical problems in case the specific rotations of the species involved are not small and their structures are rigid. Recent newly developed functionals are investigated with respect to their applicability in computations of optical rotations.

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