Electronic circular dichroism theory

Goerigk L, Grimme S (2009) Calculation of electronic circular dichroism spectra with time-dependent double-hybrid density functional theory. J Phys Chem A 113 767-776... 

Optical rotation (OR), optical rotatory dispersion (ORD), electronic circular dichroism (BCD), and vibrational circular dichroism (VCD) provide spectral information nniqne to enantiomers, allowing for the determination of absolute configuration. Recent theoretical developments in DFT, using time-dependent density fnnctional theory (TD-DFT), provide the means for computing OR, ORD, and Similar theoretical development with coupled-cluster theory,... 

Coupled oscillator models are extensions to the simple models developed for electronic circular dichroism. They are well known under the name exciton theory (see e.g. Harada and Nakanishi, 1972). These models, extended to vibrational transitions, describe the coupling of pairs of electric dipole transition moments. They predict equal amounts of positive and negative VCD intensity ... 

Electronic circular dichroism (CD) results from different absorption (molar absorption coefficient i and e ) of left- and right-circularly polarized light by the electronic subsystem of the molecule. CD has the same electronic origin as ordinary absorption. Therefore, CD spectra are interpreted in terms of the same concepts as absorption spectra, namely electronic transitions and excited states of definite chromophores For the discussions of electronic structures and excitations of complex chromophores molecular orbital (MO) theory provides an adequate framework. 

One prominent member of this class of natural products is diversonol (185), which was isolated by Turner in 1978 [128]. Its absolute configuration was determined by Krohn et al. [129] using CD spectroscopy and time dependent density functional theory calculations for electronic circular dichroism (TDDFT ECD) calculations. As discussed in Chapter 14.2, Erase et al. [71, 72] published the first enantioselective synthesis of 185 in 2011 using an anionic domino process. 

Another spectroscopy which can be addressed by (linear) response theory is electronic circular dichroism (BCD). The BCD spectrum contains a wealth of information... 

The two principal resonance limits of the theory of ROA are the far-from-resonance (FFR) limit, the original form of the theory of ROA, and the single-electronic-state (SES) limit, for the case of strong resonance between a single excited electronic state and the incident laser radiation. In the case of FFR ROA, ab initio calculations have been carried out for direct comparison with experiment. The SES theory is so simple that the complete SES-ROA spectrum can be predicted from the parent resonance Raman spectrum and the electronic circular dichroism spectrum of the resonant electronic state. 

Stephens, P.J., McCann, D.M., Devlin, F.J., and Smith, A.B.III (2006) Determination of the absolute configurations of natural products via density fimctional theory calculations of optical rotation, electronic circular dichroism, and vibrational circular didiroism the cytotoxic sesquiterpene natural products quadrone, suberosenone, suherosa-none, and suberosenol A acetate. J. Nat. Prod., 69, 1055-1064. 

Nafie LA (2004) Theory of vibrational circular dichroism and infrared absorption extension to molecules with low-lying excited electronic states. J Phys Chem A 108 7222-7231... 

---