Effects of Dispersion and Charge‐Transfer Interactions on Structures of Heavy Chalcogenide Compounds: A Quantum Chemical Case Study for (Et₂Bi)₂Te

Abstract

The reasons for the unusually small BiÀ TeÀ Bi bond angle of 86.6°observed in the crystal strucure of (Et 2 Bi) 2 Te are investigated by quantum chemical calculations. With the help of coupled cluster theory at the CCSD(T) level it is demonstrated that the structure of an isolated monomer should have a bond angle larger than 90°, despite a BiÀ Bi distance in good agreement with the value of 4.09 Å found in the crystal structure. The discrepancy is resolved by a lengthening of the BiÀ Te bond in the crystal, which is shown to be caused by partial electron transfer from neighbouring molecules to the BiÀ Te σ* orbital. Through symmetry-adapted perturbation theory at the DFT-SAPT level it is shown that London dispersion interactions are highly important for the packing of molecules in the solid state and, in turn, for the small BiÀ TeÀ Bi bond angle.