参考文献:1. Toro-Labbé A (1999) J Phys Chem A 103:4398-403 2. Jaque P, Toro-Labbé A, Politzer P, Geerlings P (2008) Chem Phys Lett 456:135-40 3. Dewar MJS (1984) J Am Chem Soc 106:209-19 CrossRef 4. Yepes D, Murray JS, Politzer P, Jaque P (2012) Phys Chem Chem Phys 14:11125-1134 CrossRef 5. Politzer P, Murray JS, Jaque P (2013) J Mol Model 19:4111-118 CrossRef 6. Toro-Labbé A, Gutiérrez-Oliva S, Concha MC, Murray JS, Politzer P (2004) J Chem Phys 121:4570-576 7. Politzer P, Burda JV, Concha MC, Lane P, Murray JS (2006) J Phys Chem A 110:756-61 8. Toro-Labbé A, Gutiérrez-Oliva S, Murray JS, Politzer P (2007) Mol Phys 105:2619-625 CrossRef 9. Burda JV, Toro-Labbé A, Gutiérrez-Oliva S, Murray JS, Politzer P (2009) J Phys Chem A 113:6500-503 10. Politzer P, Toro-Labbé A, Gutiérrez-Oliva S, Murray JS (2012) Adv Quantum Chem 64:189-10 CrossRef 11. Yepes D, Donoso-Tauda O, Pérez P, Murray JS, Politzer P, Jaque P (2013) Phys Chem Chem Phys 15:7311-320 CrossRef 12. Polanyi JC, Zewail AH (1995) Acc Chem Res 28:119-32 CrossRef 13. Zewail AH (2000) J Phys Chem A 104:5660-694 14. Yepes D, Murray JS, Pérez P, Domingo LR, Politzer P, Jaque P (2014) Phys Chem Chem Phys 16:6726-734. doi: 10.1039/c3cp54766c 15. Gutiérrez-Oliva S, Díaz, S, Toro-Labbé A, Lane P, Murray JS, Politzer P (2014) Mol Phys 112:349-54. doi: 10.1080/00268976.2013.819452 16. Herrera B, Toro-Labbé A (2004) J Chem Phys 121:7096-102 17. Bickelhaupt FM (1999) J Comput Chem 20:114-28 CrossRef 18. van Stralen JNP, Bickelhaupt FM (2006) Organometallics 25:4260-268 CrossRef 19. van Zeist W-J, Koers AH, Wolters LP, Bickelhaupt FM (2008) J Chem Theory Comput 4:920-28 20. van Zeist W-J, Bickelhaupt FM (2010) Org Biomol Chem 8:3118-127 CrossRef 21. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA et al (2003) Gaussian 03. Gaussian Inc, Wallingford, CT 22. Domingo LR, Pérez P, Sáez JA (2012) Org Biomol Chem 10:3841-851 CrossRef
作者单位:Peter Politzer (1) (2) Jane S. Murray (1) (2) Diana Yepes (3) Pablo Jaque (3)
1. CleveTheoComp LLC, 1951 W. 26th Street, Suite 409, Cleveland, OH, 44113, USA 2. University of New Orleans, New Orleans, LA, 70148, USA 3. Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Avenida República 275, Santiago, Chile
ISSN:0948-5023
文摘
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.