Related Experiment Video
Updated: Apr 23, 2026

CD Spectroscopy to Study DNA-Protein Interactions
Published on: February 10, 2022
Electronic circular dichroism of chiral alkenes: B3LYP and CAM-B3LYP calculations
Francisco E Jorge1, Sara S Jorge, Rogério N Suave
1Departamento de Física, Universidade Federal do Espírito Santo, Vitória, Brazil.
Abstract:
Time-dependent density functional theory (TDDFT) calculations of electronic circular dichroism (ECD) are widely used to determine absolute configurations (ACs) of chiral molecules. Two very popular DFT exchange-correlation functionals, one hybrid (B3LYP) and one long-range corrected (CAM-B3LYP), along with a hierarchical sequence of basis sets were investigated, and the ECD spectra predicted for eight alkenes and compared to gas-phase experimental spectra. Little variation in predicted ECD spectra was found with the basis set size enlargement, but the sensitivity to the functional is greater. Good agreement was obtained only with the CAM-B3LYP functional, leading to the conclusion that TDDFT calculations of ECD spectra can routinely provide reliable ACs if and only if an appropriate functional is used. For camphene, twistene, syn-(E)-bisfenchylidene, and phyllocladene, solvent effects were estimated.
Related Concept Videos
Properties of Enantiomers and Optical Activity
Chirality
Chiral objects exhibit a sense of handedness when they interact with another chiral object. For example, our left foot can only fit in the left shoe and not in the right shoe. Achiral objects — objects that have...
Prochirality
¹H NMR Chemical Shift Equivalence: Enantiotopic and Diastereotopic Protons
In chiral compounds such as 2-butanol, replacing the methylene hydrogens at C3 produces a pair of...
Stereoisomerism of Cyclic Compounds
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration

