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| - Density Functional Calculations on Electronic Circular DichroismSpectra of Chiral Transition Metal Complexes
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| - Time-dependent density functional theory (TD-DFT) has for the first time been applied to the computation of circulardichroism (CD) spectra of transition metal complexes, and a detailed comparison with experimental spectra hasbeen made. Absorption spectra are also reported. Various CoIII complexes as well as [Rh(en)3]3+ are studied in thiswork. The resulting simulated CD spectra are generally in good agreement with experimental spectra after correctionsfor systematic errors in a few of the lowest excitation energies are applied. This allows for an interpretation andassignment of the spectra for the whole experimentally accessible energy range (UV/vis). Solvent effects on theexcitations are estimated via inclusion of a continuum solvent model. This significantly improves the computedexcitation energies for charge-transfer bands for complexes of charge +3, but has only a small effect on those forneutral or singly charged complexes. The energies of the weak d-to-d transitions of the Co complexes aresystematically overestimated due to deficiencies of the density functionals. These errors are much smaller for the4d metal complex. Taking these systematic errors and the effect of a solvent into consideration, TD-DFT computationsare demonstrated to be a reliable tool in order to assist with the assignment and interpretation of CD spectra ofchiral transition metal complexes.
- Time-dependent density functional theory has been applied to the computation of electronic circular dichroism spectra of various chiral CoIII complexes as well as [Rh(en)3]3+. Both the d-to-d and the charge-transfer excitations were analyzed, and an assignment of the experimental spectra has been made based on this analysis. Solvent effects on the spectra have been estimated by applying a continuum solvent model in the calculations of the spectra.
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