title: Optical rotation calculated with time-dependent density functional theory: the OR45 benchmark.
abstract: Time-dependent density functional theory (TDDFT) computations are performed for 42 organic molecules and three transition metal complexes, with experimental molar optical rotations ranging from 2 to 2 × 10(4) deg cm(2) dmol(-1). The performances of the global hybrid functionals B3LYP, PBE0, and BHLYP, and of the range-separated functionals CAM-B3LYP and LC-PBE0 (the latter being fully long-range corrected), are investigated. The performance of different basis sets is studied. When compared to liquid-phase experimental data, the range-separated functionals do, on average, not perform better than B3LYP and PBE0. Median relative deviations between calculations and experiment range from 25 to 29%. A basis set recently proposed for optical rotation calculations (LPol-ds) on average does not give improved results compared to aug-cc-pVDZ in TDDFT calculations with B3LYP. Individual cases are discussed in some detail, among them norbornenone for which the LC-PBE0 functional produced an optical rotation that is close to available data from coupled-cluster calculations, but significantly smaller in magnitude than the liquid-phase experimental value. Range-separated functionals and BHLYP perform well for helicenes and helicene derivatives. Metal complexes pose a challenge to first-principles calculations of optical rotation.
authors.affiliation: Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260-3000, USA.
authors.forename: Monika
authors.initials: M
authors.lastname: Srebro
authors.forename: Niranjan
authors.initials: N
authors.lastname: Govind
authors.forename: Wibe A
authors.initials: WA
authors.lastname: de Jong
authors.forename: Jochen
authors.initials: J
authors.lastname: Autschbach
mesh_terms: D002942:Circular Dichroism; D055620:Optical Phenomena; D009930:Organic Chemicals / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D011789:Quantum Theory; D012399:Rotation; D013997:Time Factors
chemical_list: D009930:Organic Chemicals; D009942:Organometallic Compounds