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Activation enthalpies of pericyclic reactions: the performances of some recently proposed functionals

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Abstract

We have assessed the performances of three recently proposed functionals, RC (Ragot and Cortona in J Chem Phys 121:7671, 2004), TCA (Tognetti et al. in J Chem Phys 128:034101, 2008), and RevTCA (Tognetti et al. in Chem Phys Lett 460:536, 2008) by calculating the activation enthalpies for ten pericyclic reactions and eighteen 1,3-dipolar cycloadditions. We have found that the local functional (RC) gives results only marginally better than the local-density approximation ones, while the two GGA functionals, TCA and RevTCA, both strongly improve the results with respect to PBE. The performances of RevTCA, in particular, are not far different from those of a hybrid functional such as B3LYP.

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References

  1. Koch W, Holthausen MC (2000) A chemist’s guide to density functional theory. Wiley-VCH, Weinheim

    Google Scholar 

  2. Parr RG, Yang W (1989) Density functional theory of atoms and molecules. Oxford University Press, NewYork

    Google Scholar 

  3. Kohn W, Sham LJ (1965) Phys Rev 140:A1133. doi:10.1103/PhysRev.140.A1133

    Article  Google Scholar 

  4. Slater JC (1974) Quantum theory of molecules and solids. The self-consistent field for molecules and solids, vol 4. McGraw-Hill, New York

  5. Perdew JP (1991) Electronic Structure of Solids. In: Ziesche P, Eschrig H (eds) Akademie, Berlin

  6. Perdew JP, Burke K, Ernzerhof M (1996) Phys Rev Lett 77:3865. doi:10.1103/PhysRevLett.77.3865

    Article  CAS  Google Scholar 

  7. Becke AD (1988) Phys Rev A 38:3098. doi:10.1103/PhysRevA.38.3098

    Article  CAS  Google Scholar 

  8. Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785. doi:10.1103/PhysRevB.37.785

    Article  CAS  Google Scholar 

  9. Becke AD (1993) J Chem Phys 98:5648. doi:10.1063/1.464913

    Article  CAS  Google Scholar 

  10. Stephens PJ, Devlin JF, Chabalowski CF, Frisch MJ (1994) J Phys Chem 98:11623. doi:10.1021/j100096a001

    Article  CAS  Google Scholar 

  11. Colle R, Salvetti O (1975) Theor Chim Acta 37:329. doi:10.1007/BF01028401

    Article  CAS  Google Scholar 

  12. Ragot S, Cortona P (2004) J Chem Phys 121:7671. doi:10.1063/1.1792153

    Article  CAS  Google Scholar 

  13. Tognetti V, Cortona P, Adamo C (2007) Chem Phys Lett 439:381. doi:10.1016/j.cplett.2007.03.081

    Article  CAS  Google Scholar 

  14. Tognetti V, Adamo C, Cortona P (2007) Chem Phys 337:161. doi:10.1016/j.chemphys.2007.07.002

    Article  CAS  Google Scholar 

  15. Tognetti V, Cortona P, Adamo C (2008) J Chem Phys 128:034101. doi:10.1063/1.2816137

    Article  CAS  Google Scholar 

  16. Tognetti V, Cortona P, Adamo C (2008) Chem Phys Lett 460:536. doi:10.1016/j.cplett.2008.06.032

    Article  CAS  Google Scholar 

  17. Wang Y, Perdew JP (1991) Phys Rev B 43:8911. doi:10.1103/PhysRevB.43.8911

    Article  Google Scholar 

  18. Zupan A, Perdew JP, Burke K, Causà M (1997) Int J Quantum Chem 61:835. doi:10.1002/(SICI)1097-461X(1997)61:5<835::AID-QUA9>3.0.CO;2-X

    Article  CAS  Google Scholar 

  19. Zupan A, Burke K, Ernzerhof M, Perdew JP (1997) J Chem Phys 106:10184. doi:10.1063/1.474101

    Article  CAS  Google Scholar 

  20. Zhang Y, Yang W (1998) Phys Rev Lett 80:890. doi:10.1103/PhysRevLett.80.890

    Article  CAS  Google Scholar 

  21. Chan KL, Handy NC (1999) Phys Rev A 59:3075. doi:10.1103/PhysRevA.59.3075

    Article  Google Scholar 

  22. Guner VA, Khuong KS, Leach AG, Lee PS, Bartberger MD, Houk KN (2003) J Phys Chem A 107:11445. doi:10.1021/jp035501w

    Article  CAS  Google Scholar 

  23. Ess DH, Houk KN (2005) J Phys Chem A 109:9542. doi:10.1021/jp052504v

    Article  CAS  Google Scholar 

  24. Guner VA, Khuong KS, Houk KN, Chuma A, Pulay P (2004) J Phys Chem A 108:2959. doi:10.1021/jp0369286

    Article  CAS  Google Scholar 

  25. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr, Vreven T, Scalmani G, Kudin KN, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Li X, Hratchian HP, Peralta JE, Izmaylov AF, Heyd JJ, Brothers E, Staroverov V, Zheng G, Kobayashi R, Normand J, Burant JC, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Chen W, Wong MW, Pople JA (2006) Gaussian Development Version, Revision F.01. Gaussian Inc., Wallingford

  26. Montgomery JA, Frisch MJ, Ochterski JW, Peterson GA (1999) J Chem Phys 110:2822. doi:10.1063/1.477924

    Article  CAS  Google Scholar 

  27. Vosko SH, Wilk L, Nusair M (1980) Can J Phys 58:1200

    Article  CAS  Google Scholar 

  28. Joubert L, Pavone M, Barone V, Adamo C (2006) J Chem Theory Comput 2:1220. doi:10.1021/ct0600159

    Article  CAS  Google Scholar 

  29. Grimme S, Mück-Lichtenfeld C, Würthwein E-U, Ehlers AW, Goumans TPM, Lammertsma K (2006) J Phys Chem A 110:2583. doi:10.1021/jp057329x

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Laboratoire d’Electrochimie et de Chimie Analytique, UMR 7575, Ecole Nationale Supérieure de Chimie de Paris, 11 rue P. et M. Curie, 75231, Paris Cedex 05, France

    Vincent Tognetti & Carlo Adamo

  2. Laboratoire Structure, Propriété et Modélisation des Solides, UMR 8580, Ecole Centrale Paris, Grande Voie des Vignes, 92295, Châtenay-Malabry, France

    Pietro Cortona

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  1. Vincent Tognetti
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  2. Pietro Cortona
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  3. Carlo Adamo
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Correspondence to Pietro Cortona.

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Tognetti, V., Cortona, P. & Adamo, C. Activation enthalpies of pericyclic reactions: the performances of some recently proposed functionals. Theor Chem Account 122, 257–264 (2009). https://doi.org/10.1007/s00214-008-0503-y

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