Hartree-Fock and Density Functional Theory ab Initio Calculation of Optical Rotation Using GIAOs: Basis Set Dependence

J. Phys. Chem. A, 104 (5), 1039 -1046, 2000. 10.1021/jp993424s S1089-5639(99)03424-6
Web Release Date: January 15, 2000

Hartree-Fock and Density Functional Theory ab Initio Calculation of Optical Rotation Using GIAOs: Basis Set Dependence

James R. Cheeseman* and Michael J. Frisch

Gaussian, Inc., 140 Washington Avenue, North Haven, Connecticut 06473

Frank J. Devlin and Philip J. Stephens

Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482

Received: September 24, 1999

In Final Form: November 29, 1999

Abstract:

Ab initio Hartree-Fock (HF) and density functional theory (DFT) calculations of the electric dipole-magnetic dipole polarizability are reported for the chiral molecules methyloxirane (1) and trans-dimethylthiirane (2) in the static limit. Values of = ¹/₃Tr[] obtained thence are used to predict the specific optical rotations []_D of 1 and 2. Gauge-including atomic orbitals (GIAOs) are used to ensure origin independence of and []_D. and []_D values converge slowly to the complete basis set limit. Basis sets including diffuse functions are required to achieve reliable results. HF and DFT values of differ generally by 10-30%. Calculated []_D values for 1 and 2 obtained using large basis sets agree well with experimental values in sign and magnitude. The deviations can be attributed in part to the neglect of the frequency dependence of and of solvent effects.

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