Application of various population methods to some oxygenated compounds

✍ Scribed by Steven M. Bachrach; Andrew Streitwieser

• Book ID: 102878384
• Publisher: John Wiley and Sons
• Year: 1989
• Tongue: English
• Weight: 646 KB
• Volume: 10
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.540100409

✦ Synopsis

The charge on oxygen for a series of compounds was obtained using Mulliken population, natural population analysis (NPA), integrated projected electron population (IPP) analysis, and Bader's topological density analysis, "integrated Bader populations" (IBP). The orbital-based methods (Mulliken and NPA) predict oxygen charges of about -0.6 whereas the spatial-based methods (IPP and IBP) predict charges of about -1.2 to -1.3. The differences are ascribed primarily to the nuclear-centered basis sets used in the orbital methods that minimize local atomic polarization effects. Accordingly, such population analyses should be used for electronic structure considerations only with due circumspection. The IPP method as an approximation to IBP shows gross similarities; small but significant differences vary in a nonsystematic manner and IPP values must also be used with care.