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Evaluating frontier orbital energy and HOMO/LUMO gap with descriptors from density functional reactivity theory

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Abstract

Wave function theory (WFT) and density functional theory (DFT)—the two most popular solutions to electronic structure problems of atoms and molecules—share the same origin, dealing with the same subject yet using distinct methodologies. For example, molecular orbitals are artifacts in WFT, whereas in DFT, electron density plays the dominant role. One question that needs to be addressed when using these approaches to appreciate properties related to molecular structure and reactivity is if there is any link between the two. In this work, we present a piece of strong evidence addressing that very question. Using five polymeric systems as illustrative examples, we reveal that using quantities from DFT such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy, Onicescu information energy, Rényi entropy, etc., one is able to accurately evaluate orbital-related properties in WFT like frontier orbital energies and the HOMO (highest occupied molecular orbital)/LUMO (lowest unoccupied molecular orbital) gap. We verified these results at both the whole molecule level and the atoms-in-molecules level. These results provide compelling evidence suggesting that WFT and DFT are complementary to each other, both trying to comprehend the same properties of the electronic structure and molecular reactivity from different perspectives using their own characteristic vocabulary. Hence, there should be a bridge or bridges between the two approaches.

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Acknowledgements

S.B.L. and C.Y.R. acknowledge support from the National Natural Science Foundation of China (No.21503076) and RQZ is supported in part by a grant from Environmental Conservation Fund (No. 921100 (29/2015)).

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Authors and Affiliations

  1. School of Pharmacy, Hunan University of Chinese Medicine, Changsha, Hunan, 410208, China

    Ying Huang

  2. Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan, 410081, China

    Chunying Rong

  3. Department of Physics and Material Science and Center for Functional Photonics, City University of Hong Kong, Hong Kong, SAR, China

    Ruiqin Zhang

  4. Research Computing Center, University of North Carolina, Chapel Hill, NC, 27599-3420, USA

    Shubin Liu

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  1. Ying Huang
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  2. Chunying Rong
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Corresponding authors

Correspondence to Ruiqin Zhang or Shubin Liu.

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This paper belongs to Topical Collection Festschrift in Honor of Henry Chermette

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Huang, Y., Rong, C., Zhang, R. et al. Evaluating frontier orbital energy and HOMO/LUMO gap with descriptors from density functional reactivity theory. J Mol Model 23, 3 (2017). https://doi.org/10.1007/s00894-016-3175-x

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