The symmetry breaking phenomenon in heteronine analogues due to the pseudo Jahn-Teller effect

  • Ali Reza IlkhaniEmail author
Original Paper


The pseudo Jahn-Teller effect (PJTE) is employed in C8AH8 (A = O, S, Se, Te), and C8EH8 + 1 (E = N, P, As, Sb) with planar configurations to show symmetry breaking phenomena (SBP) in heteronine analogues, and to explain why molecules with (C2v) high-symmetry configurations cannot maintain planarity and pucker to their (C2) and (Cs) lower-symmetry structures, respectively. To investigate this phenomenon, geometry optimization and frequency calculations through the density functional B3LYP method using the cc-pVTZ basis set (for Te, and Sb cc-pVTZ-PP) were carried out for all compounds in the series. The state average-complete active space self-consistent field wave-function method was employed to calculate the electronic ground and several low-lying excited states to specify the adiabatic potential energy surface along the a2 and b1 puckering nuclear displacements. The PJTE (A1 + A2 + A1′) a2 and (A1 + B1 + A1′) b1 problems were formulated as the effects originating via the PJTE theorem. Moreover, replacing hydrogen atoms in C8NH9, a stable planar structure, with fluorine ligands demonstrated that SBP occur from C2v to C2 symmetry. Furthermore, thermochemical calculations via B3LY/cc-pVTZ illustrated that the planarity of the C8E ring is restored in C8EH8 (E = P, As, Sb) anions ,with the change in free energy corresponding to spontaneous deprotonation reactions as 23.67 kJ mol−1, 21.88 kJ mol−1, and 16.57 kJ mol−1, respectively. In fact, despite C8EH8 + 1 having a donor electron-pair and potentially being Lewis base compounds, it acts as a Bronsted-Lowry acid releasing a H+ proton instead in this case.


PJTE Symmetry breaking phenomenon Adiabatic potential energy surface Unstable heteronine analogues 



The author would like to acknowledge to Yazd Branch, Islamic Azad University for the financial support of this research. This work has been enabled in part by support from Westgrid ( and Compute/Calcul Canada (


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of ChemistryYazd Branch, Islamic Azad UniversityYazdIran
  2. 2.Department of ChemistryUniversity of AlbertaEdmontonCanada

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