Study of the potential energy surface of reactions in a system containing i-propyl and n-propyl radicals

Capa

Citar

Texto integral

Acesso aberto Acesso aberto
Acesso é fechado Acesso está concedido
Acesso é fechado Somente assinantes

Resumo

The energy pathways of possible decomposition and isomerization reactions of iso-propyl (i-C3H7) and n-propyl (n-C3H7) radicals have been studied by computational methods of quantum chemistry. B3LYP, M062X, MP2, and CBS-QB3 methods are used to localize stationary points on the potential energy surface of a system containing propyl radicals. A number of intermediate compounds formed during the isomerization and decomposition of propyl radicals have been identified, and information has been obtained on their structure and thermochemical parameters. Based on the results of the research, a diagram of the energy levels of the system under consideration was constructed.

Texto integral

Acesso é fechado

Sobre autores

A. Davtyan

Institute of Chemical Physics by A.B. Nalbandyan, National Academy of Sciences of Republic of Armenia

Email: arsentiev53@mail.ru
Armênia, Yerevan

Z. Manukyan

Institute of Chemical Physics by A.B. Nalbandyan, National Academy of Sciences of Republic of Armenia

Email: arsentiev53@mail.ru
Armênia, Yerevan

S. Arsentev

Institute of Chemical Physics by A.B. Nalbandyan, National Academy of Sciences of Republic of Armenia

Autor responsável pela correspondência
Email: arsentiev53@mail.ru
Armênia, Yerevan

L. Tavadyan

Institute of Chemical Physics by A.B. Nalbandyan, National Academy of Sciences of Republic of Armenia

Email: arsentiev53@mail.ru
Armênia, Yerevan

V. Arutyunov

Semenov Federal Research Center for Chemical Physics of Russian Academy of Sciences

Email: arsentiev53@mail.ru
Rússia, Moscow

Bibliografia

  1. A. Ushakova, V. Zatsepin, M. Varfolomeev, D. Emelyanov, J. Combust. 11, 1 (2017). https://doi.org/
  2. A. A. Mantashyan, Russ. J. Phys. Chem. B 15, 233 (2021). https://doi.org/10.1134/S1990793121020214
  3. N. M. Pogosyan, M. Dj. Pogosyan, S. D. Arsentiev, et al., Petroleum Chemi. 60 (3), 316 (2020). https://doi.org/
  4. R. R.Grigoryan, S. D. Arsentev, Petr. Chem. 60 (2), 187 (2020). https://doi.org/
  5. A. S. Palankoeva, A. A. Belyaev, V. S. Arutyunov, Russ. J. Phys. Chem. B 16 (3), 399 (2022). https://doi.org/
  6. S. D. Arsentev, L. A. Tavadyan, M. G. Bryukov, et al., Russ. J. Phys. Chem. B 16 (6), 1019 (2022). https://doi.org/10.1134/S1990793122060021
  7. A. V. Ozerskii, A. D. Starostin, A. V. Nikitin, V. S. Arutyunov, Combust. Explosion 15 (1), 30 (2022). https://doi.org/10.30826/CE22150104
  8. A. D. Becke, Phys. Rev. A. 38, 3098 (1988).
  9. A. D. Becke, J. Chem. Phys. 98, 5648 (1993).
  10. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 37, 785 (1988).
  11. Y. Zhao, D. G. Truhlar, Theor. Chem. Account. 120, 215 (2008). https://doi.org/
  12. Y. Zhao, D. G. Truhlar, Acc. Chem. Res. 41, 157 (2008). https://doi.org/
  13. M. J. Frisch, M. Head-Gordon, J. A. Pople, Chem. Phys. Lett. 166 (3), 275 (1990). https://doi.org/
  14. M. Head-Gordon, J. A. Pople, M. J. Frisch, Chem. Phys. Lett. 153 (6), 503 (1988). https://doi.org/10.1016/0009-2614(88)85250-3
  15. Jr. J. A. Montgomery, M. J. Frisch, J. W. Ochterski, G. A. Petersson, J. Chem. Phys. 110, 2822 (1999).
  16. M. R. Nyden, G. A. Petersson, J. Chem. Phys. 75, 1843 (1981).
  17. G. A. Petersson, M. A. Al-Laham, J. Chem. Phys. 94, 6081 (1991).
  18. G. A. Petersson, T. G. Tensfeldt, J. A. Montgomery, J. Chem. Phys. 94, 6091 (1991).
  19. Jr. J. A. Montgomery, M. J. Frisch, J. W. Ochterski, G. A. Petersson, J. Chem. Phys. 112, 6532 (2000). https://doi.org/10.1063/1.481224
  20. S. D. Arsentev, A. A. Mantashyan, React. Kinet. Catal. Lett. 13 (2), 125 (1980). https://doi.org/
  21. A. A. Mantashyan, L. A. Khachatryan, O. M. Niazyan, S. D. Arsentev, Combust. Flame 43, 221 (1981). https://doi.org/
  22. A. A. Mantashyan, N. G. Edigaryan, L. A. Khachatryan, S. D. Arsentev, High Energ. Chem. 23 (1), 63 (1989).
  23. R. R. Grigoryan, S. D. Arsentev, Pet. Chem. 60 (2) 187 (2020). https://doi.org/
  24. A. H. Davtyan, Z. O. Manukyan, S. D. Arsentev, L. A. Tavadyan, V. S. Arutyunov, Russ. J. Phys. Chem. B 17 (2), 336 (2023). https://doi.org/10.1134/S1990793123020239
  25. M. K. Ghosh, S. N. Elliott, K. P. Somers, S. J. Klippenstein, H. J. Curran, Combust. Flame 112492 (2022). https://doi.org/10.1016/j.combustflame.2022.112492
  26. M. S. Stark, J. Am. Chem. Soc. 122 (17) 4162 (2000). https://doi.org/
  27. L. K. Huynh, H.-H. Carstensen, A. M. Dean, J. Phys. Chem. A 114 (24), 6594 (2010). https://doi.org/10.1021/jp1017218
  28. M. Cord, B. Husson, J. C. L. Huerta, O. Herbinet, et al., J. Phys. Chem. A. 116 (50), 12214 (2012). https://doi.org/10.1021/jp309821z
  29. Zh. Yang, X. Lin, B. Long, W. Zhang, Chem. Phys. Lett. 749, 137442 (2020). https://doi.org/10.1016/j.cplett.2020.137442
  30. J. A. Miller, S. J. Klippenstein, J. Phys. Chem. A 117 (13), 2718 (2013). https://doi.org/10.1021/jp312712p
  31. N. N. Buravtsev, Russ. J. Phys. Chem. B 16 (2), 218 (2022). https://doi.org/10.1134/S1990793122020038
  32. A. Ramalingam, S. Panigrahy, Y. Fenard, H. Curran, K. A. Heufer, Combust. Flame 223 (1), 361 (2021). https://doi.org/
  33. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox, Gaussian 16, Revision C.01, Gaussian, Inc., Wallingford CT, 2016.
  34. R. Dennington, T. A. Keith, J. M. Millam GaussView, Version 6.1, Semichem Inc., Shawnee Mission, KS. 2019.
  35. R. Ditchfield, W. J. Hehre, J. A. Pople, J. Chem. Phys. 54 (2), 724 (1971). https://doi.org/10.1063/1.1674902
  36. T. H. Dunning, J. Chem. Phys. 90 (2), 1007 (1989). https://doi.org/10.1063/1.456153
  37. H. B. Schlegel, J. Comp. Chem. 3, 214 (1982). https://doi.org/
  38. C. Peng, P. Y. Ayala, H. B. Schlegel, M. J. Frisch, J. Comp. Chem. 17 (1), 49 (1996). https://doi.org/10.1002/(SICI)1096-987X(19960115)17:1<49::AID-JCC5>3.0.CO;2-0
  39. C. Peng, H. B. Schlegel, Israel J. Chem. 33, 449 (1993).
  40. K. Fukui, Acc. Chem. Res. 14, 363 (1981). https://doi.org/
  41. H. P. Hratchian, H. B. Schlegel, Theory and Applications of Computational Chemistry: The First 40 Years. Eds. C. E. Dykstra, G. Frenking, K. S. Kim, G. Scuseria Elsevier, Amsterdam, 2005, P. 195.
  42. W.-Y. Chen, T.-N. Nguyen, M.-C. Lin, N.-S. Wang, H. Matsui, Intern. J. Chem. Kinetics. 53, 646 (2021). https://doi.org/10.1002/kin.21471
  43. W. E. Falconer, W. A. Sunder, Int. J. Chem. Kinet. 3, 523 (1971). https://doi.org/
  44. E. P. F. Lee, T. G. Wright, J. Phys. Chem. A 103 (6), 721 (1999). https://doi.org/10.1021/jp983236m
  45. D. V. Chicharro, S. M. Poullain, A. Zanchet, et al., Chem. Sci. 10 (26), 6494 (2019). https://doi.org/10.1039/c9sc02140j
  46. R. S. Zhu, Z. F. Xu, M. C. Lin, J. Chem. Phys. 120 (14), 6566 (2004). https://doi.org/10.1063/1.1665370
  47. J. E. Baldwin, L. S. Day, S. R. Singer, J. Am. Chem. Soc. 127 (26), 9370 (2005). https://doi.org/10.1021/ja052678q

Arquivos suplementares

Arquivos suplementares
Ação
1. JATS XML
Baixar
2. Fig. 1. Total energy diagram of intermediates relative to i-C3H7 calculated by the M062X/6-311+G(2d,p) method. TS1–TS6 are transition states; CH3CCH3-1 and CH3CCH3-2 are two conformers of dimethylcarbene.

Baixar (167KB)
Metadados
3. Fig. 2. Transition state of the isomerization reaction i-C3H7 → n-C3H7 calculated by the M062X/6-311+G(2d,p) method.

Baixar (52KB)
Metadados
4. Fig. 3. Spatial structures of free radicals localized on the PES of a system containing i-propyl and n-propyl radicals. The multiplicity of the molecular structure is indicated in brackets.

Baixar (92KB)
Metadados

Declaração de direitos autorais © Russian Academy of Sciences, 2024