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Accuracy of auxiliary density functional theory hybrid calculations for activation and reaction enthalpies of pericyclic reactions

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Abstract

Auxiliary density functional theory (ADFT) hybrid calculations are based on the variational fitting of the Coulomb and Fock potential and, therefore, are free of four-center electron repulsion integrals. So far, ADFT hybrid calculations have been validated successfully for standard enthalpies of formation. In this work the accuracy of ADFT hybrid calculations for the description of pericyclic reactions was quantitatively validated at the B3LYP/6-31G*/GEN-A2* level of theory. Our comparison with conventional Kohn-Sham density functional theory (DFT) results shows that the DFT and ADFT activation and reaction enthalpies are practically indistinguishable. A systematic study of various functionals (PBE, B3LYP, PBE0, CAMB3LYP, CAMPBE0 and HSE06) and basis sets (6-31G*, DZVP-GGA and aug-cc-pVXZ; X = D, T and Q) revealed that the ADFT HSE06/aug-cc-pVTZ/GEN-A2* level of theory yields best balanced accuracy for the activation and reaction enthalpies of the studied pericyclic reactions. With the successfully validate ADFT composite approach consisting of PBE/DZVP-GGA/GEN-A2* structure and transition state optimizations and single-point HSE06/aug-cc-pVTZ/GEN-A2* energy calculations, an accurate, reliable and efficient computational approach for the study of pericyclic reactions in systems at the nanometer scale is proposed.

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Acknowledgments

JRGP and FAD gratefully acknowledge funding as a Sistema Nacional de Investigadores (SNI) assistant (15228) and Consejo Nacional de Ciencia y Tecnología (CONACyT) PhD fellow (421457), respectively. This work was financially supported by the CONACyT Project CB-252658 and by the infrastructure Project GIC-268251. The authors are also thankful to Q.I. Luis Lopez-Sosa for valuable discussions.

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Authors and Affiliations

  1. Departamento de Química, CINVESTAV, Centro de Investigación y de Estudios Avanzados, Av. Instituto Politécnico Nacional 2508, A.P. 14-740, 07000, México D.F, Mexico

    José R. Gómez-Pérez, Patrizia Calaminici & Andreas M. Köster

  2. Programa de Doctorado en Nanociencias y Nanotecnología, CINVESTAV, Instituto Politécnico Nacional 2508, A.P. 14-740, 07000, Ciudad de México, Mexico

    Francisco A. Delesma, Patrizia Calaminici & Andreas M. Köster

Authors
  1. José R. Gómez-Pérez
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  2. Francisco A. Delesma
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  3. Patrizia Calaminici
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  4. Andreas M. Köster
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Corresponding authors

Correspondence to Patrizia Calaminici or Andreas M. Köster.

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This paper belongs to Topical Collection International Conference on Systems and Processes in Physics, Chemistry and Biology (ICSPPCB-2018) in honor of Professor Pratim K. Chattaraj on his sixtieth birthday

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Gómez-Pérez, J.R., Delesma, F.A., Calaminici, P. et al. Accuracy of auxiliary density functional theory hybrid calculations for activation and reaction enthalpies of pericyclic reactions. J Mol Model 24, 223 (2018). https://doi.org/10.1007/s00894-018-3759-8

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  • DOI: https://doi.org/10.1007/s00894-018-3759-8

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