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An examination of density functional theories on isomerization energy calculations of organic molecules

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Abstract

Long-range corrected (LC) density functional theories (DFTs) were applied to the isomerization energy calculations of organic molecules to make clear why conventional DFTs including B3LYP have given poor isomerization reaction energies. Combining with local response dispersion (LRD) method, we performed LC-DFT calculations for the benchmark set of isomerization reactions. Consequently, we found that LC-DFT + LRD methods give accurate reaction energies equivalent to up-to-date DFTs containing many semi-empirical parameters. This result indicates that long-range exchange and intramolecular dispersion correlation interactions, which have been neglected in conventional DFTs, play prominent roles in isomerization reactions. However, we also found that these interactions are not sufficient to give accurate isomerization energies especially for cyclization reactions. Considering that Gaussian-attenuated LC-DFTs (LCgau-DFTs) give better isomerization reaction energies than LC-DFTs, we suggested that the isomerization energies will be further improved by correcting the short-range part of exchange functionals in DFT with keeping the whole long-range exchange interactions.

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Acknowledgments

We would like to pay honors to Prof. Imamura for his great achievements. This research was supported by the Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT) (Grants: 20350002 and 20038012). The numerical calculations were conducted on the RIKEN Cluster of Clusters (RICC). One of the authors (JWS) is indebted to a post-doctoral fellowship for foreign researchers from the Japan Society for the Promotion of Science (JSPS). Another author (TT) would like to thank Canon Inc. and Hitachi Chemical Co. Ltd for their contributions.

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Authors and Affiliations

  1. Department of Chemical System Engineering, School of Engineering, The University of Tokyo, Tokyo, 113-8656, Japan

    Jong-Won Song

  2. CREST, Japan Science and Technology Agency, Saitama, 332-0012, Japan

    Jong-Won Song, Takao Tsuneda & Kimihiko Hirao

  3. Advanced Science Institute, RIKEN 2-1, Hirosawa, Wako, Saitama, 351-0198, Japan

    Takao Tsuneda & Kimihiko Hirao

  4. Photon Science Center of the University of Tokyo, Tokyo, 113-8656, Japan

    Takeshi Sato

Authors
  1. Jong-Won Song
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  2. Takao Tsuneda
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  3. Takeshi Sato
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  4. Kimihiko Hirao
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Corresponding author

Correspondence to Takao Tsuneda.

Additional information

Dedicated to Professor Akira Imamura on the occasion of his 77th birthday and published as part of the Imamura Festschrift Issue.

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Song, JW., Tsuneda, T., Sato, T. et al. An examination of density functional theories on isomerization energy calculations of organic molecules. Theor Chem Acc 130, 851–857 (2011). https://doi.org/10.1007/s00214-011-0997-6

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