Add time:08/09/2019         Source:sciencedirect.com

Fourier transform infrared spectra of MnO4− anions isomorphously isolated in potassium perchlorate matrices were recorded at room and low temperature (LT, ∼100 K). On the basis of the detected second-order vibrational transitions involving the dopant species ν3 mode components, anharmonicity constants and harmonic eigenvalues for these modes were calculated. Despite the fact that, rigorously speaking, the appearance of the spectra of dopant permanganate anions may be explained in terms of a Cs site symmetry, the ν3 stretching region resembles an approximate A1⊕E splitting (characteristic for a local C3v or even higher symmetry), which is not expected, even within the latent symmetry approach. We explain such spectral patterns on the basis of vibrational mode mixing (a ‘Fermi-like’ resonance) of the MnO4− ν1 mode with the ν3a site-group component. With the results of degenerate case stationary perturbation theory, we show that in the present case the Fermi-like resonance is predominantly responsible for the observed spectral features. The appearance of the region of second-order vibrational transitions in the spectra of dopant permanganate anions may be better explained in terms of the (rigorous) crystallographic Cs site group (corresponding to the crystallographic Pnma space group), instead of the ‘latent’ (effective) symmetry site group C2v (corresponding to the latent symmetry space group Imma).

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