Revisited vibronic model for Li+ ion and F A (Li) centre in alkali halides

Summary The controversial far-infrared optical absorption in Li-doped alkali halides is now attributed to transitions between the low-lying energy levels of an anharmonic oscillator composed of three halogen-ion pairs centred at the cation site which vibrate in theT _1u ungerade mode. This oscillator is electronically coupled to the impurity dragging it into rotation over 〈111〉 sites. Several experimental features derive simply from our model such as the absence of any clear-cut lithium-isotope effect and the low-frequency range. The capital effect of an F centre at a 〈001〉 nearest-neighbour (nn) site is to reduce the dimensionality of vibration forcing the impurity to rotate in the perpendicular (001)-plane. This upgrades the optical frequency in proportion to (3/2)^1/2 and shrinks the off-centre displacement. We finally show that recent computer-simulation data on Li-doped alkali halides provide a solid ground for regarding the Li off-centredness as a pseudo-Jahn-Teller phenomenon. Due to the relevance of its scientific content, this paper has been given priority by the Journal Direction.