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Driving and retarding forces in a chemical reaction

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Abstract

The reaction force F(ξ) is the negative gradient of the potential energy of a chemical process along the intrinsic reaction coordinate ξ. We extend the rigorous concept of F(ξ) to the “activation strain model” of Bickelhaupt et al., to formulate the “strain” force F str(ξ) that retards a reaction and the “interaction” force F int(ξ) that drives it. These are investigated for a group of Diels-Alder cycloadditions. The results fully support the interpretation of the minimum of F(ξ) as defining the beginning of the transition from deformed reactants to eventual products.

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References

  1. Toro-Labbé A (1999) J Phys Chem A 103:4398–4403

    Google Scholar 

  2. Jaque P, Toro-Labbé A, Politzer P, Geerlings P (2008) Chem Phys Lett 456:135–140

    CAS  Google Scholar 

  3. Dewar MJS (1984) J Am Chem Soc 106:209–219

    Article  CAS  Google Scholar 

  4. Yepes D, Murray JS, Politzer P, Jaque P (2012) Phys Chem Chem Phys 14:11125–11134

    Article  CAS  Google Scholar 

  5. Politzer P, Murray JS, Jaque P (2013) J Mol Model 19:4111–4118

    Article  CAS  Google Scholar 

  6. Toro-Labbé A, Gutiérrez-Oliva S, Concha MC, Murray JS, Politzer P (2004) J Chem Phys 121:4570–4576

    Google Scholar 

  7. Politzer P, Burda JV, Concha MC, Lane P, Murray JS (2006) J Phys Chem A 110:756–761

    CAS  Google Scholar 

  8. Toro-Labbé A, Gutiérrez-Oliva S, Murray JS, Politzer P (2007) Mol Phys 105:2619–2625

    Article  Google Scholar 

  9. Burda JV, Toro-Labbé A, Gutiérrez-Oliva S, Murray JS, Politzer P (2009) J Phys Chem A 113:6500–6503

    CAS  Google Scholar 

  10. Politzer P, Toro-Labbé A, Gutiérrez-Oliva S, Murray JS (2012) Adv Quantum Chem 64:189–210

    Article  CAS  Google Scholar 

  11. Yepes D, Donoso-Tauda O, Pérez P, Murray JS, Politzer P, Jaque P (2013) Phys Chem Chem Phys 15:7311–7320

    Article  CAS  Google Scholar 

  12. Polanyi JC, Zewail AH (1995) Acc Chem Res 28:119–132

    Article  CAS  Google Scholar 

  13. Zewail AH (2000) J Phys Chem A 104:5660–5694

    CAS  Google Scholar 

  14. Yepes D, Murray JS, Pérez P, Domingo LR, Politzer P, Jaque P (2014) Phys Chem Chem Phys 16:6726–6734. doi: 10.1039/c3cp54766c

  15. Gutiérrez-Oliva S, Díaz, S, Toro-Labbé A, Lane P, Murray JS, Politzer P (2014) Mol Phys 112:349–354. doi: 10.1080/00268976.2013.819452

  16. Herrera B, Toro-Labbé A (2004) J Chem Phys 121:7096–7102

    CAS  Google Scholar 

  17. Bickelhaupt FM (1999) J Comput Chem 20:114–128

    Article  CAS  Google Scholar 

  18. van Stralen JNP, Bickelhaupt FM (2006) Organometallics 25:4260–4268

    Article  Google Scholar 

  19. van Zeist W-J, Koers AH, Wolters LP, Bickelhaupt FM (2008) J Chem Theory Comput 4:920–928

    Google Scholar 

  20. van Zeist W-J, Bickelhaupt FM (2010) Org Biomol Chem 8:3118–3127

    Article  Google Scholar 

  21. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA et al (2003) Gaussian 03. Gaussian Inc, Wallingford, CT

    Google Scholar 

  22. Domingo LR, Pérez P, Sáez JA (2012) Org Biomol Chem 10:3841–3851

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The activation strain model of Bickelhaupt et al. was brought to our attention by Professor Bickelhaupt’s presentation in the Virtual Conference on Computational Chemistry (VCCC-2013) organized by Professor Ponnadurai Ramasami. We would like to express our appreciation to both of them. The authors also acknowledge Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT) through the project N° 1100291. D.Y. thanks La Comisión Nacional de Investigación Científica y Tecnológica (CONICYT) for a PhD fellowship.

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Authors and Affiliations

  1. CleveTheoComp LLC, 1951 W. 26th Street, Suite 409, Cleveland, OH, 44113, USA

    Peter Politzer & Jane S. Murray

  2. University of New Orleans, New Orleans, LA, 70148, USA

    Peter Politzer & Jane S. Murray

  3. Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Avenida República 275, Santiago, Chile

    Diana Yepes & Pablo Jaque

Authors
  1. Peter Politzer
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  2. Jane S. Murray
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  3. Diana Yepes
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  4. Pablo Jaque
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Corresponding author

Correspondence to Peter Politzer.

Additional information

This paper belongs to Topical Collection MIB 2013 (Modeling Interactions in Biomolecules VI)

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Politzer, P., Murray, J.S., Yepes, D. et al. Driving and retarding forces in a chemical reaction. J Mol Model 20, 2351 (2014). https://doi.org/10.1007/s00894-014-2351-0

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  • DOI: https://doi.org/10.1007/s00894-014-2351-0

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