Density Functional Computations of Vibrational Circular Dichroism Spectra beyond the Born-Oppenheimer Approximation

Journal of Chemical Theory and Computation
Josef Tomecek, Petr Bouř

Abstract

Transition metal complexes provide rich features in vibrational circular dichroism (VCD) spectra, including significant intensity enhancements, and become thus useful in structural and functional studies of molecules. Quite often, however, the vibrational spectral bands are mixed with the electronic ones, and interpretation of such experiments is difficult. In the present study, we elaborate the theory needed to calculate the VCD intensities beyond the Born-Oppenheimer (BO) approximation. Within a perturbation approach, the coupling between the electronic and vibrational states is estimated using the harmonic approximation and simplified wavefunctions obtainable from common density functional theory (DFT) computations. Explicit expressions including Slater determinants and derivatives of molecular orbitals are given. On a model diamine complex, the implementation is tested and factors affecting spectral intensities and frequencies are investigated. For two larger molecules, the results are in a qualitative agreement with previous experimental data. Typically, the electronic-vibrational interaction Hamiltonian coupling elements are rather small (~0-10 cm-1), which provides negligible contributions to vibrational frequencies and ...Continue Reading

References

Jun 11, 2005·The Journal of Chemical Physics·Marco CaricatoJacopo Tomasi
Feb 28, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Christian Johannessen, Peter W Thulstrup
Feb 11, 2014·Journal of the American Chemical Society·Sérgio R DomingosSander Woutersen
Mar 10, 2009·Journal of Chemical Theory and Computation·Vincenzo BaroneFabrizio Santoro
Jan 25, 2019·The Journal of Physical Chemistry Letters·Gennaro PescitelliLorenzo Di Bari

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