Generation of basis sets with high degree of fulfillment of the Hellmann-Feynman theorem

✍ Scribed by J. Fernández Rico; R. López; I. Ema; G. Ramírez

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 301 KB
• Volume: 28
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20601

✦ Synopsis

Abstract

A direct relationship is established between the degree of fulfillment of the Hellman‐Feynman (electrostatic) theorem, measured as the difference between energy derivatives and electrostatic forces, and the stability of the basis set, measured from the indices that characterize the distance of the space generated by the basis functions to the space of their derivatives with respect to the nuclear coordinates. On the basis of this relationship, a criterion for obtaining basis sets of moderate size with a high degree of fulfillment of the theorem is proposed. As an illustrative application, previously reported Slater basis sets are extended by using this criterion. The resulting augmented basis sets are tested on several molecules finding that the differences between energy gradient and electrostatic forces are reduced by at least one order of magnitude. © 2007 Wiley Periodicals, Inc. J Comput Chem 28: 748–758, 2007