AB Initio Electronic Circular Dichroism and Optical Rotatory Dispersion: From Organic Molecules to Transition Metal Complexes

Good Computational Practice in the Assignment of Absolute Configurations by TDDFT Calculations of ECD Spectra

“…We have only discussed TDDFT as the method of choice for running ECD calculations, in view of its present great popularity. However, several other methods are feasible for excited‐state calculations that represent useful alternatives to TDDFT, especially in some circumstances . Although conventional TDDFT is very time‐effective, it is not feasible to calculate the ECD of larger molecules.…”

“…Not surprisingly, then, nonempirical methods of analysis such as the exciton chirality have become quickly popular and spurred much research . The revolution, or renaissance, of chiroptical spectroscopies, however, arrived when the ab initio theoretical simulation of chiroptical properties, including ECD, optical rotation (OR), vibrational CD (VCD), Raman optical activity (ROA), and so on, became a concrete possibility for real‐life molecules such as natural products and transition metal complexes . Quantum‐mechanical (QM) calculations of chiroptical spectra make it possible to assign AC's without the need for any reference system or any chemical derivatization, and often without the necessity of establishing the molecular physicochemical mechanisms responsible for the observed property (the so‐called mechanisms of optical activity).…”

Origin invariance in vibrational resonance Raman optical activity

“…[1][2][3][4][5][6] The latter techniques have gained increasing interest recently as valuable tools for assigning the absolute configurations and for obtaining information on the local environment of oscillating modes of molecular systems and on conformational ratios important in determining reactivities of biomolecules. 5,7 The tremendous progress of ab initio quantum chemistry in such a field has been reflected in the larger number of applications of QM approaches to the calculation of chiroptical properties and spectroscopies.…”

Phytotoxins produced by Phoma chenopodiicola, a fungal pathogen of Chenopodium album

“…1) by acetylation with pyridine and acetic anhydride. The IR spectrum of 4 showed the absence of any hydroxy group band while its 1 H NMR spectrum ( The absolute configuration of (À)-1 was determined by ab initio computational analyses of its ORD and ECD spectra (Autschbach, 2009(Autschbach, , 2012. This approach was demonstrated to be particularly straightforward and reliable for the absolute configuration assignment of natural products (Mazzeo et al, 2013;Santoro et al, 2013Santoro et al, , 2014.…”