Structural, vibrational, and bonding analysis of M2SiO (M=Li or Ag) using density functional theory

✍ Scribed by M. E. Alikhani

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 144 KB
• Volume: 71
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(1999)71:6<499::aid-qua7>3.0.co;2-2

✦ Synopsis

The spectroscopic properties of the M -SiO M ϭ Li or Ag complexes 2 were studied using density functional theory. It is shown that the global minimum of Li -SiO corresponds to a doubly bridged silonyl structure, while that of Ag -SiO is a 2 2 phosgenelike structure. The calculated binding energies of the M -SiO complexes 2 relative to M q SiO are y47.8 and y4.0 kcal mol y1 for M ϭ Li and Ag, respectively. In 2 the case of Ag -SiO, the calculated SiO stretching frequency as well as its isotopic shifts 2 are in good agreement with the experimental data. For Li -SiO, the SiO vibrational 2 y1 Ž . frequency is calculated to be greatly red-shifted by 493.4 cm f 40% of free upon SiO complexation. According to the natural population analysis, the charge transfer from metal to ligand is 0.79 e y for each Li and is only of 0.15 e y for each Ag. The bonding was also investigated using the topological analysis of the charge density.