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What dictates alkane isomerization? A combined density functional theory and information-theoretic approach study

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Abstract

Alkanes are deceptively simple in their geometric structures, yet their electronic structures are a tough nut to crack. We employ two total energy partition schemes in density functional theory and the information-theoretic approach quantities to dissect the so-called isomerization problem. From our validation results, we have found theoretical methods, basis sets, dispersion corrections, and numerical integration grids all make contributions to the total energy difference. We highly recommend that PBE0-D3(BJ)/def2-QZVPP is a good choice for studying the longer alkane isomerization issue. We further find that the electrostatic potential dominates the isomerization of alkanes, provided that empirical dispersion is added. This conformational flexibility can be easily explained in the framework of conceptual density functional theory. This observation contrasts the commonly held belief that electron delocalization dictates alkane isomerization. We also find that molecular polarizability can be linearly correlated with some ITA quantities (such as Shannon entropy and Fisher information), indicating that simple density-based functions can be good descriptors of molecular properties.

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Acknowledgements

It is a pleasure to dedicate this work to Professor Pratim Kumar Chattaraj on his 65th birthday. This work is supported by the start-up funding of Yunnan university and the Yunnan Fundamental Research Projects (Grant No. 202101AU070012).

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Author notes

  1. Chenyu Luo and Xin He have contributed equally.

Authors and Affiliations

  1. School of Pharmaceutical and Chemical Engineering, Taizhou University, Linhai, 318000, Zhejiang, People’s Republic of China

    Chenyu Luo & Aiguo Zhong

  2. Qingdao Institute for Theoretical and Computational Sciences, Institute of Frontier and Interdisciplinary Science, Shandong University, Qingdao, 266237, Shandong, People’s Republic of China

    Xin He

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

    Shubin Liu

  4. Department of Chemistry, University of North Carolina, Chapel Hill, NC, 27599-3290, USA

    Shubin Liu

  5. Institute of Biomedical Research, Yunnan University, Kunming, 650500, Yunnan, People’s Republic of China

    Dongbo Zhao

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  1. Chenyu Luo
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  3. Aiguo Zhong
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Contributions

A.Z., S.L., and D.Z. contributed to conceptualization; C.L. and X.H. performed data curation; C.L. and X.H. carried out formal analysis; D.Z. contributed to funding acquisition; A.Z., S.L., and D.Z. performed project administration; A.Z., S.L., and D.Z. performed supervision; C.L. and X.H. performed writing—original draft; A.Z., S.L., and D.Z. performed writing—review and editing.

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Correspondence to Aiguo Zhong, Shubin Liu or Dongbo Zhao.

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Luo, C., He, X., Zhong, A. et al. What dictates alkane isomerization? A combined density functional theory and information-theoretic approach study. Theor Chem Acc 142, 78 (2023). https://doi.org/10.1007/s00214-023-03014-8

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