Spectroscopic and electrooptical manifestations of internal rotation of the outer-sphere cation in Li(PO3) molecule

Spectroscopic and electrooptical manifestations of internal molecular rotations in LiPO3 have been studied on the basis of ab initio calculated surface of potential energy and dipole momentum function using the finite element method. It has been ascertained that tunnel splitting of energy levels with number n, available for vibrational spectroscopy of high resolution, apper in the molecule studied only at n≥13. It is shown that internal rotations in the molecule are able to decrease sharply its polarity on vibration-excited levels, sufficiently far from the vertex of potential barrier of intramolecular regroupings. Difficulties of experimental confirmation of predicted electrooptical effect of structural non-rigidity in the molecule studied are discussed