Electron Pair Localization Function (EPLF) for Density Functional Theory and ab Initio Wave Function-Based Methods: A New Tool for Chemical Interpretation

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• 作者：Anthony Scemama ; Michel Caffarel ; Robin Chaudret ; Jean-Philip Piquemal
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2011
• 出版时间：March 8, 2011
• 年：2011
• 卷：7
• 期：3
• 页码：618-624
• 全文大小：895K
• 年卷期：v.7,no.3(March 8, 2011)
• ISSN：1549-9626

文摘

We present a modified definition of the Electron Pair Localization Function (EPLF), initially defined within the framework of quantum Monte Carlo approaches [Scemama, A.; Caffarel, M.; Chaquin, P. J. Chem. Phys. 2004, 121, 1725] to be used in Density Functional Theories (DFT) and ab initio wave-function-based methods. This modified version of the EPLF鈥攚hile keeping the same physical and chemical contents鈥攊s built to be analytically computable with standard wave functions or Kohn鈭扴ham representations. It is illustrated that the EPLF defines a simple and powerful tool for chemical interpretation via selected applications including atomic and molecular closed-shell systems, 蟽 and 蟺 bonds, radical and singlet open-shell systems, and molecules having a strong multiconfigurational character. Some applications of the EPLF are presented at various levels of theory and compared to Becke and Edgecombe鈥檚 Electron Localization Function (ELF). Our open-source parallel software implementation of the EPLF opens the possibility of its use by a large community of chemists interested in the chemical interpretation of complex electronic structures.