On the performance of density functional methods for describing atomic populations, dipole moments and infrared intensities

✍ Scribed by Frank De Proft; Jan M.L. Martin; Paul Geerlings

• Publisher: Elsevier Science
• Year: 1996
• Tongue: English
• Weight: 591 KB
• Volume: 250
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(96)00057-7

✦ Synopsis

Atomic populations according to the Mulliken, electrostatic, natural population, and atomic polar tensor (APT) definitions were evaluated for first-and second-row compounds using different correlated ab initio techniques, DFT methods, and basis sets. All definitions except MuUiken exhibit modest basis set sensitivity. B3LYP predicts partial charges in agreement with high-level ab initio results. Exact-exchange corrections are more important than gradient corrections for this property. B3LYP with at least sdpf basis sets usually predicts dipole moments and infrared intensities in agreement with more accurate calculations, while semiquantitative IR intensities are obtained even with the modest cc-pVDZ basis set.