Optical rotation calculations on large molecules using the approximate coupled cluster model CC2 and the resolution-of-the-identity approximation

Daniel H. Friesea, Christof Hättigb,
a Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N+9037 Tromsø, Norway
a Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44801 Bochum, Germany

Phys. Chem. Chem. Phys. 16, 5942-5951 (2014), in press, DOI:10.1039/C3CP54338B
(Received 14th October 2013; accepted 27th November 2013)

We investigate the performance of the approximate coupled cluster singles- and doubles model CC2 for the prediction of optical rotations for organic molecules. For this purpose we employ a combination of two tests sets from the literature which include small and medium-sized rigid organic molecules and a series of helicenes. CC2 calculations on molecules as large as 11-helicene became possible through a recent implementation of frequency-dependent second-order properties for CC2 which makes use of the resolution-of-the-identity approximation for the electron repulsion integrals. The results are assessed with respect to the accuracy of the absolute values of the optical rotation and the prediction of the correct sign, which is crucial for the determination of absolute configurations. The performance of CC2 is compared with that of density functional theory at the B3LYP and CAM-B3LYP levels. Furthermore we investigated the influence of the molecular geometry and the one-electron basis set and tested to which extent spin-component scaling changes the results.

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