Are There Atomic Orbitals in a Molecule?

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• 作者：I. Mayer ; I. Bak贸 ; A. Stirling
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：November 17, 2011
• 年：2011
• 卷：115
• 期：45
• 页码：12733-12737
• 全文大小：760K
• 年卷期：v.115,no.45(November 17, 2011)
• ISSN：1520-5215

文摘

Effective atomic orbitals (AOs) have been calculated by the method of the 鈥渇uzzy atoms鈥?analysis by using the numerical molecular orbitals (MOs) obtained from plane-wave DFT calculation, i.e., without introducing any atom-centered functions. The results show that in the case of nonhypervalent atoms there are as many effective AOs with non-negligible occupation numbers, as many orbitals are in the classical minimal basis set of the given atom. This means that, for nonhypervalent systems, it is possible to present the MOs as sums of effective atomic orbitals that resemble very much the atomic minimal basis orbitals of the individual atoms (or their hybrids). For hypervalent atoms some additional orbitals basically of d-type are also of some importance; they are necessary to describe the back-donation to these positive atoms. It appears that the d-type orbitals play a similar role also for strongly positive carbon atoms. The method employed here is also useful to decide whether the use of polarization functions of a given type is a matter of conceptual importance or has only a numerical effect.