Canonical orthonormalization and neglect of differential overlap

✍ Scribed by Harry F. King; Marshall D. Newton; Richard E. Stanton

• Book ID: 103012899
• Publisher: Elsevier Science
• Year: 1975
• Tongue: English
• Weight: 416 KB
• Volume: 31
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(75)80059-5

✦ Synopsis

L&din's canonical orthonormalization procedure is non-unique ifthe o-/erlap matrix has degenerate eigenvalues. A re-.cent attempt-by Roby to justify neglect of differential overlap is re-examinrd taking proper account of this lack of uniqueness. We conclude that his central result, eq. ( 6) in our paper, is formally correct in the limit of complete basis sets, but Rdby'a presentationlends a misleading interpretation to this equation. Consequently, some conclusions which are claimed --to follow are, in fact, not valid. We briefly investigate the Roby approximation for finite basis sets and indicate the strengths and weaknesses when used for practical computations.