Physical Chemistry Chemical Physics 2012-06-07

Localized optimized orbitals, coupled cluster theory, and chiroptical response properties.

Harley R McAlexander, Taylor J Mach, T Daniel Crawford

Index: Phys. Chem. Chem. Phys. 14(21) , 7830-6, (2012)

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Abstract

The impact of orbital localization on the efficiency and accuracy of the optimized-orbital coupled cluster model is examined for the prediction of chiroptical properties, in particular optical rotation. The specific rotations of several test cases-(P)-[4]triangulane, (S)-1-phenylethanol, and chiral conformers of 1-fluoropentane, heptane, and nonane-were computed using an approach in which localization is enforced throughout the orbital optimization and subsequent linear response computation. This method provides a robust local-correlation scheme for future production-level implementation. Although the cross-over point between the canonical and localized coupled cluster approach lies at larger molecules than for ground-state energies, the scheme presented should still provide reduced scaling sufficient to investigate much larger molecules than are presently accessible.