Infrared spectra of permanganate anions in potassium perchlorate matrices: vibrational anharmonicity, effective symmetry and vibrational mode mixing effects.
Fourier transform infrared spectra of MnO4- anions isomorphously isolated in potassium perchlorate matrices were recorded at room and low temperature (LT, approximately 100 K). On the basis of the detected second-order vibrational transitions involving the dopant species nu3 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 nu3 stretching region resembles an approximate A1+E splitting (characteristic for a local C3nu 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- nu1 mode with the nu3, 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 C2nu (corresponding to the latent symmetry space group Imma).
Pejov
Ljupco
L
Faculty of Science, Institute of Chemistry, Sts. Cyril and Methodius University, PO Box 162, 1001 Skopje, Macedonia. ljupcop@iunona.pmf.ukim.edu.mk
Petrusevski
Vladimir M
VM
D017895:Manganese Compounds / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry*; D010472:Perchlorates / Q000737:chemistry*; D017680:Potassium Compounds / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
D017895:Manganese Compounds; D010087:Oxides; D010472:Perchlorates; D017680:Potassium Compounds; C048856:permanganic acid; C009006:potassium perchlorate