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Atomistic sp3d5s* tight-binding theory of PbSe and PbS nanocrystals is developed. It is demonstrated, that the valley splittings of confined electrons and holes strongly and peculiarly depend on the geometry of a nanocrystal. When the nanocrystal lac ks a microscopic center of inversion and has T_d symmetry, the splitting is strongly suppressed as compared to the more symmetric nanocrystals with O_h symmetry, having an inversion center.
We propose a mechanism of energy relaxation for carriers confined in a non-polar quantum dot surrounded by an amorphous polar environment. The carrier transitions are due to their interaction with the oscillating electric field induced by the local v ibrations in the surrounding amorphous medium. We demonstrate that this mechanism controls energy relaxation for electrons in Si nanocrystals embedded in a SiO$_2$ matrix, where conventional mechanisms of electron-phonon interaction are not efficient.
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