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

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Abstract

Ab initio Hartree−Fock (HF) and density functional theory (DFT) calculations of the electric dipole−magnetic dipole polarizability βαβ are reported for the chiral molecules methyloxirane (1) and trans-dimethylthiirane (2) in the static limit. Values of β = 1/3Tr[βαβ] obtained thence are used to predict the specific optical rotations [α]D of 1 and 2. Gauge-including atomic orbitals (GIAOs) are used to ensure origin independence of β and [α]D. β and [α]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 βαβ differ generally by 10−30%. Calculated [α]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 β and of solvent effects.

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