Density-functional theory calculations of optical rotatory dispersion in the nonresonant and resonant frequency regions

• Published in: The Journal of chemical physics Vol. 120; no. 11; p. 5027
• Main Authors: Norman, Patrick, Ruud, Kenneth, Helgaker, Trygve
• Format: Journal Article
• Language: English
• Published: United States 15.03.2004
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.1647515

The complex linear response function, which can be employed for calculations of second-order molecular properties in regions of strong absorption, is here extended to encompass the mixed electric-dipole-magnetic-dipole polarizability. The mixed electric-dipole-magnetic-dipole polarizability determines the optical rotation and, when absorption is taken into account, the full anomalous optical rotatory dispersion (ORD) spectra of chiral molecules can be calculated using first-principle quantum-chemical methods. Gauge-origin independence of the results is ensured through the use of London atomic orbitals. To illustrate the importance of taking the absorption process properly into account, we here apply this methodology to the study of the anomalous ORD of hydrogen peroxide, 3R-methylcyclohexanone, 4R-1,1-dimethyl-[3]-(1,2)-ferrocenophan-2-on, and the D(2) isomer of the C(84) fullerene.