EPR investigation of NO2 and CO2 − and other radicals in beryl

Abstract

A number of different impurities are located in the open channels of natural beryl crystals. The rare Maxixe beryl contains an unusual amount of NO2. The isoelectronic CO2 − radical is found in the irradiated Maxixe-type beryl. The NO2 radicals are distributed in the Be–Al plane of the crystal, with the nitrogen atom close to the oxygens of the beryl cavity wall. These oxygens repel the negative CO2 − radical, which is located at the center of the beryl cavity and rotates around its O–O axis, which is parallel to the crystal c-axis. When there is a nearby alkali ion at the center of the beryl channel, it reorients the CO2 − radical so that its bisector is parallel to the c-axis and points toward the positive ion. Different signals are analyzed for Li+, Na+, and another counter-ion, which probably is Cs+. The related NO3 and CO3 − radicals are the color centers in the investigated deep blue beryls. The slow decay of the color, which makes these beryls useless as gem stones, is related to the decay of the hydrogen atoms which are present in these crystals. Evidence is given that NO3 is created in Maxixe beryl by a natural process, while CO3 − in Maxixe-type beryl has been created by irradiation. The temperature dependence of the EPR signals of these two radicals was investigated, but a definitive proof that they rotate at the center of the beryl cavity could not be given. EPR signals from some other radicals in beryl have been observed and described.