Journal of Structural Chemistry

, Volume 60, Issue 5, pp 736–745 | Cite as

Computational Investigation of the Pseudo Jahn–Teller Effect on the Structure and Chemical Properties of Perhaloethene Anions

  • G. Mahmoudzadeh
  • R. GhiasiEmail author
  • H. Pasdar


The instability of planar structures in [C2X4] (X = H, F, Cl, Br) molecules due to the pseudo Jahn-Teller effect (PJTE) is investigated as an original PJTE study. Optimization and the following frequency calculations in these molecules illustrate that all of these compounds are unstable in high symmetry planar (with D2h symmetry) geometry and their structures are distorted to a lower C2h symmetry stable geometry. Moreover, the vibronic coupling interaction between 2B2g ground and 2Ag excited states via the (2B2g + 2Ag) ⊗B2g PJTE problem is the reason for the symmetry breaking phenomenon and non-planarity in those series. Natural bond analysis (NBO) is used for illustrating the strongest interaction and natural atomic charges of these structures.


perhaloethene anions pseudo Jahn-Teller effect (PJTE) symmetry breaking phenomena vibronic coupling constant natural bond analysis (NBO) 


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  1. 1.
    R. A. King, N. D. Pettigrew, and H. F. Schaefer. J. Chem. Phys., 1997, 107, 8536.CrossRefGoogle Scholar
  2. 2.
    X.-J. Hou and M.-B. Huang. J. Phys. Chem. A, 2002, 106, 10655.CrossRefGoogle Scholar
  3. 3.
    M. N. Paddon-Row, N. G. Rondan, K. N. Houk, and K. D. Jordan. J. Am. Chem. Soc., 1982, 104, 1143.CrossRefGoogle Scholar
  4. 4.
    S. Merry and C. Thomson. Chem. Phys. Lett., 1981, 82, 373.CrossRefGoogle Scholar
  5. 5.
    J. T. Wang and F. Williams. J. Am. Chem. Soc., 1981, 103, 2902.CrossRefGoogle Scholar
  6. 6.
    R. I. McNeil, M. Shiotani, F. Williams, and M. B. Yim. Chem. Phys. Lett., 1977, 51, 433.CrossRefGoogle Scholar
  7. 7.
    J. R. Morton, K. F. Preston, J. T. Wang, and F. Williams. Chem. Phys. Lett., 1979, 64, 71.CrossRefGoogle Scholar
  8. 8.
    M. N. Paddon-Row, N. G. Rondan, K. N. Houk, and K. D. Jordan. J. Am. Chem. Soc., 1982, 104, 1143.CrossRefGoogle Scholar
  9. 9.
    Topics in Molecular Organization and Engineering / Eds. A. Lund, M. Shiotani. Dordrecht: Springer Science and Business Media, 1991, 6.Google Scholar
  10. 10.
    I. B. Bersuker. The Jahn-Teller Effect. Cambridge University Press, 2006.Google Scholar
  11. 11.
    R. G. Pearson. Symmetry Rules for Chemical Reactions. Wiley-Interscience: New York, 1976.Google Scholar
  12. 12.
    A. R. Ilkhani. Russ. J. Phys. Chem. A, 2017, 91, 1743.CrossRefGoogle Scholar
  13. 13.
    Y. Shen and J. J. BelBruno. J. Phys. Chem. A, 2005, 109, 512.CrossRefGoogle Scholar
  14. 14.
    P. Garcia-Fernandez, J. A. Aramburu, M. Moreno, M. Zlatar, and M. G-Pavlovic. J. Chem. Theory Comput., 2014, 10, 1824.CrossRefGoogle Scholar
  15. 15.
    X.-J. Feng, M. Zhang, L.-X. Zhao, H.-Y. Zhang, and Y.-H. Luo. Comput. Theor. Chem., 2014, 1029, 84.CrossRefGoogle Scholar
  16. 16.
    A. R. Ilkhani. J. Mol. Struct., 2015, 1098, 21.CrossRefGoogle Scholar
  17. 17.
    Y. Liu. Comput. Theor. Chem., 2014, 1044, 94.CrossRefGoogle Scholar
  18. 18.
    F. Grein. Theor. Chem. Ace, 2014, 133, 1482.CrossRefGoogle Scholar
  19. 19.
    Y. Kameoka, T. Sato, T. Koyama, K. Tanaka, and T. Kato. Chem. Phys. Lett., 2014, 598, 69.CrossRefGoogle Scholar
  20. 20.
    A. R. Ilkhani. J. Theor. Comput. Chem., 2015, 14, 1550045.CrossRefGoogle Scholar
  21. 21.
    N. N. Gorinchoy, I. I. Balan, and I. B. Bersuker. Comput. Theor. Chem., 2011, 976(2011), 113.CrossRefGoogle Scholar
  22. 22.
    M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalman, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox. Revision A.02 ed., Gaussian, Inc.: Wallingford CT, 2009.Google Scholar
  23. 23.
    F. Weigend and R. Ahlrichs. Phys. Chem. Chem. Phys., 2005, 7, 3297.CrossRefGoogle Scholar
  24. 24.
    C. C. J. Roothaan. Rev. Mod. Phys., 1951, 23, 69.CrossRefGoogle Scholar
  25. 25.
    J. A. Pople and R. K. Nesbet. J. Chem. Phys., 1954, 22, 571.CrossRefGoogle Scholar
  26. 26.
    R. McWeeny and G. Dierksen. J. Chem. Phys., 1968, 49, 4852.CrossRefGoogle Scholar
  27. 27.
    J. B. Foresman, M. Head-Gordon, J. A. Pople, and M. J. Frisch. J. Phys. Chem. A, 1992, 96, 135.CrossRefGoogle Scholar
  28. 28.
    A. E. Reed, L. A. Curtiss, and F. Weinhold. Chem. Rev., 1988, 88, 899.CrossRefGoogle Scholar
  29. 29.
    E. D. Glendening, J. K. Badenhoop, A. E. Reed, J. E. Carpenter, J. A. Bohmann, C. M. Morales, C. R. Landis, and F. Weinhold. Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 2013.Google Scholar
  30. 30.
    L. Pauling. The Nature of the Chemical Bond. 3rd ed. Cornell University Press: Ithaca, 1960.Google Scholar
  31. 31.
    P. W. Ayers and R. G. Parr. J. Am. Chem. Soc., 2000, 422, 2010.CrossRefGoogle Scholar
  32. 32.
    R. G. Parr and P. K. Chattaraj. J. Am. Chem. Soc., 1991, 113, 1854.CrossRefGoogle Scholar
  33. 33.
    R. G. Pearson. J. Chem. Educ., 1987, 64, 561.CrossRefGoogle Scholar
  34. 34.
    R. G. Pearson. Acc. Chem. Res., 1993, 26, 250.CrossRefGoogle Scholar
  35. 35.
    R. G. Pearson. J. Chem. Educ., 1999, 76, 267.CrossRefGoogle Scholar
  36. 36.
    E. Chamorro, P. K. Chattaraj, and P. Fuentealba. J. Phys. Chem. A, 2003, 107, 7068.CrossRefGoogle Scholar
  37. 37.
    R. Parthasarathi, M. Elango, V. Subramanian, and P. K. Chattaraj. Theor. Chem. Acc., 2005, 113, 257.CrossRefGoogle Scholar
  38. 38.
    P. A. Christiansen and W. E. Palke. J. Chem. Phys., 1977, 67, 57.CrossRefGoogle Scholar
  39. 39.
    V. F. Weisskopf. Science, 1975, 187, 605.CrossRefGoogle Scholar
  40. 40.
    J. K. Badenhoop and F. Weinhold. Int. J. Quantum. Chem., 1999, 72, 269.CrossRefGoogle Scholar

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© Pleiades Publishing, Ltd. 2019

Authors and Affiliations

  1. 1.Department of Chemistry, Arak BranchIslamic Azad UniversityArakIran
  2. 2.Department of Chemistry, East Tehran BranchIslamic Azad UniversityTehranIran
  3. 3.Faculty of Chemistry, North Tehran BranchIslamic Azad UniversityTehranIran

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