title: Localized optimized orbitals, coupled cluster theory, and chiroptical response properties.
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.
authors.affiliation: Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, USA.
authors.forename: Harley R
authors.initials: HR
authors.lastname: McAlexander
authors.forename: Taylor J
authors.initials: TJ
authors.lastname: Mach
authors.forename: T Daniel
authors.initials: TD
authors.lastname: Crawford