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We present a detailed picture of the electronic structure of donor-vacancy complexes in Ge-doped silicon and Si-doped germanium Clusters to mimic Si-rich and Ge-rich SiGe alloys, respectively Jahn-Teller effects and electrical levels were investigated in both Si-rich and Ge-rich end compositions It is shown that while Ge atoms act as efficient traps for mobile E-centers in Si-rich alloys, Si atoms in Ge-rich material do not have this ability A detailed linear combination of atomic orbitals model is proposed for VP-Ge and VP-Si complexes in Si1-xGex and Ge1-xSix, where the orbital filling order is driven by the larger electron affinity of Si atoms when compared to Ge. (C) 2009 Elsevier B.V. All rights reserved