Fermi resonances of borohydrides in a crystalline environment of alkali metals.
Vibrational spectra of BH(4)(-) and its isotopic analogues in a crystalline environment of alkali metals cations (K(+), Rb(+), Cs(+)) have been investigated beyond the harmonic approximation using a variational approach supported by computations of B3LYP type anharmonic force fields. From the comparison of the observed and simulated IR spectra, the influence of the anharmonic couplings on the band position and on the relative intensity of the allowed vibrational transitions is discussed. Here, the effect of the crystalline environment induces a blue shift of about 50 and 100 cm(-1) respectively for the bending and stretching modes of BH(4)(-). Furthermore, anharmonic effects, which are exclusively well reproduced by a variational approach, are needed to yield reliable positions and relative amplitudes of IR allowed combination and overtone transitions. This leads to theoretical results fitting their experimental counterpart between 6 and 30 cm(-1) in the investigated series.
Carbonnière
Philippe
P
Laboratoire de Chimie Théorique et Physico-Chimie Moléculaire, UMR 5624, Fédération de Recherche IPREM 2606, Université de Pau et des Pays de l'Adour, IFR Rue Jules Ferry, 64000 Pau, France. philippe.carbonniere@univ-pau.fr
Hagemann
Hans
H