A theoretical method for calculating magnetic circular dichroism (MCD) of molecules is presented. We examined the numerical accuracy and the stability of the finite perturbation (FP) method and the sum-over-state (SOS) perturbation method. The relativistic effects are shown to be important for the MCD spectra of molecules containing heavy elements. Calculations using the FP and the SOS methods were carried out for ethylene, para- and ortho-benzoquinone, showing that the FP method is superior to the SOS method, as expected. The relativistic effect was examined using the second-order Douglas-Kroll Hamiltonians for the halogen molecules , , , and . The Faraday terms of and were strongly affected by the relativistic effects, while the effect was negligible for and .
Theoretical studies on magnetic circular dichroism by the finite perturbation method with relativistic corrections
Y. Honda, M. Hada, M. Ehara, H. Nakatsuji, J. Michl; Theoretical studies on magnetic circular dichroism by the finite perturbation method with relativistic corrections. J. Chem. Phys. 22 October 2005; 123 (16): 164113. https://doi.org/10.1063/1.2080027
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