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Study of organic reactions using chemical reactivity descriptors derived through a temperature-dependent approach

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Using the ratio of two fluctuations in the temperature-dependent density functional theory, the local counterpart of a global response function and the linear (non-local) counterpart of a local response function can be constructed. Here, we analyze the local chemical potential, local hardness, Fukui kernel and dual descriptor kernel and test their performance for describing and interpreting reactivity features for a diverse set of organic chemical reactions, including acid–base reactions, aliphatic nucleophilic substitutions, aromatic electrophilic substitutions and Markovnikov additions. Despite important differences in size and functionalization between some substrates belonging to a given chemical reaction type, temperature-dependent chemical reactivity descriptors were able to reproduce experimental or computational trends in all cases. We identify relevant chemical interactions belonging to a particular family of reactions and the molecular moieties responsible for such interactions. In general, our results are consistent with traditional chemical interpretations. However, in some cases the information contained in the temperature-dependent chemical reactivity descriptors allows one to gain new insights about the organic chemistry reactions considered here.

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We thank the Laboratorio Nacional de Cómputo de Alto Desempeño for the use of their facilities through the Laboratorio de Supercómputo y Visualización of Universidad Autónoma Metropolitana-Iztapalapa. PWA and MFP thank NSERC, the Canada Research Chairs, Compute Canada, and Canarie for support. MFP also thanks Universidad Autónoma Metropolitana-Iztapalapa for a visiting professor invitation. JLG and AV thank Conacyt for Grants 237045 and Fronteras-867, respectively. CPR was supported in part by Conacyt through a doctoral fellowship.

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Correspondence to Marco Franco-Pérez or José L. Gázquez.

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Franco-Pérez, M., Polanco-Ramírez, C.A., Gázquez, J.L. et al. Study of organic reactions using chemical reactivity descriptors derived through a temperature-dependent approach. Theor Chem Acc 139, 44 (2020).

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  • Temperature-dependent reactivity indicators
  • Organic reactions
  • Local chemical potential
  • Local hardness
  • Fukui kernel
  • Dual descriptor kernel