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.

Molecular Dipole Moments within the Incremental Scheme Using the Domain-Specific Basis-Set Approach

“…Significant contribution in this area was done by Werner, Schütz and coworkers, [29][30][31][32][33][34][35][36] who utilized the 3 Pulay-Saebø approach, 24,25 as well as by Neese et al, who realized the local pair-naturalorbital (LPNO) approach. [37][38][39][40][41][42] Other methods are based on fragmentation schemes, which divide the whole system into parts [66][67][68][69] and frequency-dependent polarizabilities. 6,69 In this work the incremental scheme of is used for the calculation of molecular dipole moments.…”

A molecular orbital selection approach for fast calculations of specific rotation with density functional theory

“…Crawford et al extended the local correlation idea of Pulay and Saebø to response properties and then later implemented it for [ α ] ω calculations . This method uses localized orbitals and neglects interactions between distant orbitals, thus reducing the cost of the correlation part of the calculation . While this method is successful for smaller systems, the authors show that for larger systems the need for tighter thresholds outweighs the benefits of neglecting parts of the wave function …”

“…25 This method uses localized orbitals and neglects interactions between distant orbitals, thus reducing the cost of the correlation part of the calculation. 26,27 While this method is successful for smaller systems, the authors show that for larger systems the need for tighter thresholds outweighs the benefits of neglecting parts of the wave function. 25 In this work, we present a different approach to reduce the cost of [α] ω calculations with Kohn-Sham DFT (KS-DFT), based on the selection of the molecular orbitals (MOs) that are likely to contribute the most to this property and discarding the rest.…”

Incremental evaluation of coupled cluster dipole polarizabilities

“…61. [70][71][72] In this work we apply the incremental scheme of Stoll [73][74][75] to compute the CCSD frequency-dependent dipole polarizabilities. Within the Pulay-Saebø framework, Werner, Schütz, Korona, and co-workers 62-64 have carried out locally correlation coupled cluster computations of dipole moments, static polarizabilities, and excitation energies at the CCSD level, while Schütz and co-workers have reported local second-order CC (CC2) computations of transition properties, excitation energies, and excited-state dipole moments.…”