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An ab initio MO study of selenium sulfide heterocycles Se S8−

1998; Elsevier BV; Volume: 453; Issue: 1-3 Linguagem: Inglês

10.1016/s0166-1280(98)00202-4

1872-7999

Jari Taavitsainen, Heidi Lange, Risto S. Laitinen,

Chalcogenide Semiconductor Thin Films

Abstract The structures and relative stabilities of Se n S 8− n ring molecules have been studied by the use of ab initio molecular orbital techniques using MIDI-4* basis sets for atomic orbitals. Full geometry optimizations have been carried out for all 30 isomers at HF level of theory, and the fundamental vibrations have been calculated to ascertain the nature of the stationary point. Each molecule lies at a local minimum and is a crown-shaped eight-membered ring like S 8 . The calculated bond parameters indicate single bonds and agree with experimental information where available. The relative stabilities of the different isomers have been calculated at the MP2 level of theory including the correction for the zero-point vibrational energy. The total binding energies of the molecular species decrease with increasing selenium content in the moleules. By contrast, the energies of the different isomers with the same chemical compositions are virtually identical. All Se n S 8− n species show very similar valence electronic structures. The energies of the 16 highest occupied molecular orbitals that represent the chalcogen–chalcogen bonding orbitals and the p lone-pair orbitals of the chalcogen atoms are affected very little by the nature of the chalcogen atoms in the molecule. On the other hand, the energies of the next eight molecular orbitals that represent the s lone-pair orbitals of the chalcogen atoms increase with the selenium content of the molecule. A selection of interconversion reactions between the different Se n S 8− n rings demonstrates that the energy change in the transformation of one S–S and one Se–Se bond into two Se–S bonds is very small (ca. 1 kJ mol −1 ) in agreement with the experimental evidence. This small energy difference together with the similarities in the valence electronic structures of the S–S, Se–S and Se–Se bonds is consistent with the observation that most preparative routes lead to a complicated molecular mixture of different selenium sulfides.