Density functional study of platinum polyyne monomer, oligomer, and polymer: Ground state geometrical and electronic structures

作者：Motaghiani Shahram^*; Mirabbaszadeh Kavoos

来源：International Journal of Quantum Chemistry, 2013, 113(11): 1650-1659.

DOI：10.1002/qua.24380

• platinum polyyne
• density functional method
• electronic structure
• finite oligomer approach
• charge delocalization

Geometries of monomers and oligomers of a platinum polyyne and its free ligands were optimized using density functional theory with B3LYP hybrid functional. The LANL2DZ basis set was used for Pt and the 6-31G* for other atoms in geometry optimizations. The electronic structures of these compounds were analyzed using Stuttgart/Dresden ECPs (SDD) basis set for metal atoms and 6-311G* for others. The polymerization has very little effect on the bond lengths and by introducing the metal, the acetylide bond length increases slightly. The strong overlap between metal spx orbitals and sigma px orbitals of acetylides results in localized sigma bonding. The hybridization between the ligand p orbitals and the platinum d orbital resulted in the -conjugation enhancement. This conjugation enhancement causes some effects such as the highest-occupied molecular orbitallowest-unoccupied molecular orbital gap reduction and charge transfer characteristic of low-energy vertical transitions.

• 出版日期2013-6-5