Einleitung / Introduction

Lehl, Herbert; Buschbeck, Karl-Christian; Gagarin, Rostislaw

doi:10.1007/978-3-662-12164-1_1

Cited by 1 publication

(1 citation statement)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Consider first the tris-bidentate complex ion [Co(en) 3 ] 3+ ( 42 ). Its molar rotation was estimated to be −383 on the basis of optical rotatory dispersion (ORD) measured for a solution of its tris-chloride salt . As the augD data of Table show, at each level of methodology considered here agreement with experiment is rather poor, with all the functionals overestimating the magnitude.…”

Section: Resultsmentioning

confidence: 99%

Optical Rotation Calculated with Time-Dependent Density Functional Theory: The OR45 Benchmark

et al. 2011

View full text Add to dashboard Cite

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.

show abstract

Section: Resultsmentioning

confidence: 99%