Advertisement

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

  • Ali Reza IlkhaniEmail author
Original Paper
  • 17 Downloads

Abstract

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.

Keywords

PJTE Symmetry breaking phenomenon Adiabatic potential energy surface Unstable heteronine analogues 

Notes

Acknowledgments

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 (http://www.westgrid.ca) and Compute/Calcul Canada (http://www.computecanada.ca).

References

  1. 1.
    Anastassiou AG, Cellura RP (1969) 1-Oxacyclonona-2,4,6,8-tetraene (oxonin). Chem Comm 16:903–904CrossRefGoogle Scholar
  2. 2.
    Anastassiou AG, Cellura RP (1969) Oxonin; thermal and photochemical bond relocation. Chem Comm 24:1521–1522CrossRefGoogle Scholar
  3. 3.
    Anastassiou AG, Gebrian JH (1970) 1-H azonin. Tetrahedron Lett 11:825–827CrossRefGoogle Scholar
  4. 4.
    Anastassiou AG, Eachus SW, Cellura RP, Gebria JH (1970) The question of aromaticity in the heteronins. Chem Comm 18:1133–1135CrossRefGoogle Scholar
  5. 5.
    Anastassiou AG (1975) Synthesis and study of select heterocycles. Pure Appl Chem 44:691–749CrossRefGoogle Scholar
  6. 6.
    Huckel E (1931) Quantentheoretische Beitrage zum Benzol problem. Z Phys 70:204–286CrossRefGoogle Scholar
  7. 7.
    Anastassiou AG (1972) Heteronins. Acc Chem Res 5:281–288CrossRefGoogle Scholar
  8. 8.
    Rabinovitz M, Cohen Y (1988) Probing the nature of polycyclic conjugated dianions: from carbocyclic to heterocyclic dianions: NMR studies, π-delocalization and electronic structure. Tetrahedron 44:6957–6994CrossRefGoogle Scholar
  9. 9.
    Chiang CC, Paul IC, Anastassiou AG, Eachus SW (1974) Molecular structure of an N-substituted azonine. Demonstration of polyenic character in a member of this class of compounds. J Am Chem Soc 96:1636–1638CrossRefGoogle Scholar
  10. 10.
    Somers KRF, Kryachko ES, Ceulemans A (2004) Azonine, a “nearly” forgotten aromatic molecule. J Phys Chem A 108:4059–4068CrossRefGoogle Scholar
  11. 11.
    Bersuker IB (2006) The Jahn-Teller effect. Cambridge University Press, Cambridge, UKCrossRefGoogle Scholar
  12. 12.
    Bersuker IB (2013) Pseudo Jahn-Teller effect—a two-state paradigm in formation, deformation, and transformation of molecular systems and solids. Chem Rev 113:1351–1390CrossRefGoogle Scholar
  13. 13.
    Ilkhani AR (2017) The symmetry breaking phenomenon in 1,2,3-trioxolene and C2Y3Z2 (Y= O, S, se, Te, Z= H, F) compounds: a pseudo Jahn-Teller origin study. Quim Nova 40:491–495Google Scholar
  14. 14.
    Kim JH, Lee Z (2014) Silicene on other two-dimensional materials: formation of Heterostructure. Appl Microscopy 44:123–132CrossRefGoogle Scholar
  15. 15.
    Gromov EV, Trofimov AB, Vitkovskaya NM, Schirmer J, Koppel H (2003) Theoretical study of the low-lying excited singlet states of furan. J Chem Phys 119:737–753CrossRefGoogle Scholar
  16. 16.
    Blancafort L, Bearpark MJ, Robb MA (2006) Ring puckering of cyclooctatetraene and cyclohexane is induced by pseudo-Jahn-Teller coupling. Mol Phys 104:2007–2010CrossRefGoogle Scholar
  17. 17.
    Ilkhani AR (2015) Pseudo Jahn-Teller origin of twisting in 3, 6-pyridazinedione derivatives; N2C4H2Y2Z2 (Y = O, S, se, Z = H, F, cl, Br) compounds. J Theo Comput Chem 1550045(1–14):6Google Scholar
  18. 18.
    Liu Y, Bersuker IB, Garcia-Fernandez P, Boggs JE (2012) Pseudo Jahn-Teller origin of nonplanarity and rectangular-ring structure of tetrafluorocyclobutadiene. J Phys Chem A 116:7564–7570CrossRefGoogle Scholar
  19. 19.
    Soto JR, Molina B, Castro JJ (2015) Reexamination of the origin of the pseudo Jahn-Teller puckering instability in silicene. Phys Chem Chem Phys 17:7624–7628CrossRefGoogle Scholar
  20. 20.
    Hermoso W, Ilkhani AR, Bersuker IB (2014) Pseudo Jahn-Teller origin of instability of planar configurations of hexa-heterocycles C4N2H4X2 (X = H, F, cl, Br). Comput Theo Chem 1049:109–114CrossRefGoogle Scholar
  21. 21.
    Ilkhani AR (2017) Pseudo Jahn-Teller effect in Oxepin, azepin, and their halogen substituted derivatives. Russian J Phys Chem A 91:1743–1751CrossRefGoogle Scholar
  22. 22.
    Bersuker IB (2017) Manipulation of structure and properties of two-dimensional systems employing the pseudo Jahn-Teller effect. FlatChem 6:11–27CrossRefGoogle Scholar
  23. 23.
    Ilkhani AR, Hermoso W, Bersuker IB (2015) Pseudo Jahn-Teller origin of instability of planar configurations of hexa-heterocycles. Application to compounds with 1,2- and 1,4-C4X2 skeletons (X= O, S, se, Te). Chem Phys 460:75–82CrossRefGoogle Scholar
  24. 24.
    Gorinchoy NN, Bersuker IB (2017) Pseudo Jahn-Teller effect in control and rationalization of chemical transformations in two-dimensional compounds. J Phys Con Series 833:012010Google Scholar
  25. 25.
    Ilkhani AR, Monajjemi M (2015) The Pseudo Jahn-Teller effect of puckering in pentatomic unsaturated rings C4AE5, a= N, P, as, E= H, F, cl. Comput Theo Chem 1074:19–25CrossRefGoogle Scholar
  26. 26.
    Hermoso W, Liu Y, Bersuker IB (2014) Novel effect induced by pseudo-Jahn-Teller interactions: broken cylindrical symmetry in linear molecules. J Chem Theo Comput 10:4377–4388CrossRefGoogle Scholar
  27. 27.
    Jose D, Datta A (2011) Structures and electronic properties of silicene clusters: a promising material for FET and hydrogen storage. Phys Chem Chem Phys 13:7304–7311CrossRefGoogle Scholar
  28. 28.
    Chowdhury C, Jahiruddin S, Datta A (2016) Pseudo-Jahn-Teller distortion in two-dimensional phosphorus: origin of black and blue phases of phosphorene and band gap modulation by molecular charge transfer. J Phys Chem Lett 7:1288–1297CrossRefGoogle Scholar
  29. 29.
    Ivanov AS, Miller E, Boldyrev AI, Kameoka Y, Sato T, Tanaka K (2015) Pseudo Jahn-Teller origin of buckling distortions in two-dimensional Triazine-based graphitic carbon nitride (g-C3N4) sheets. J Phys Chem C 119:12008–12015CrossRefGoogle Scholar
  30. 30.
    Pokhodnya K, Olson C, Dai X, Schulz DL, Boudjouk P, Sergeeva AP, Boldyrev AI (2011) Flattening a puckered cyclohexasilane ring by suppression of the pseudo-Jahn-Teller effect. J Chem Phys 134:1–5CrossRefGoogle Scholar
  31. 31.
    Ivanov AS, Bozhenko KV, Boldyrev AI (2012) On the suppression mechanism of the pseudo-Jahn-Teller effect in middle E6 (E = P, as, Sb) rings of triple-decker sandwich complexes. Inorg. Chem. 51:8868–8872CrossRefGoogle Scholar
  32. 32.
    Ilkhani AR (2015) Pseudo Jahn-Teller origin of puckering in cyclohexahomoatomic molecules E6 (S, se, Te) and restoring S6 planar ring configuration. J Mol Struc 1098:21–25CrossRefGoogle Scholar
  33. 33.
    Sergeeva AP, Boldyrev AI (2010) Flattening a puckered pentasilacyclopentadienide ring by suppression of the pseudo Jahn-Teller effect. Organometallics 29:3951–3954CrossRefGoogle Scholar
  34. 34.
    Ilkhani AR, Gorinchoy NN, Bersuker IB (2015) Pseudo Jahn-Teller effect in distortion and restoration of planar configurations of tetra-heterocyclic 1,2-diazetes C2N2E4, E = H, F, Cl, Br. Chem Phys 460:106–110CrossRefGoogle Scholar
  35. 35.
    Polly R, Werner HJ, Manby FR, Knowles PJ (2004) Fast Hartree-Fock theory using local density fitting approximations. Mol Phys 102:2311–2321CrossRefGoogle Scholar
  36. 36.
    Wilson AK, Woon DE, Peterson KA, Dunning TH (1999) Gaussian basis sets for use in correlated molecular calculations. IX. The atoms gallium through krypton. J Chem Phys 110:7667–7676CrossRefGoogle Scholar
  37. 37.
    Dunning TH (1989) Gaussian basis sets for use in correlated molecular calculations. I. the atoms boron through neon and hydrogen. J Chem Phys 90:1007–1023CrossRefGoogle Scholar
  38. 38.
    Woon DE, Dunning TH (1993) Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon. J Chem Phys 98:1358–1371CrossRefGoogle Scholar
  39. 39.
    Peterson KA (2003) Systematically convergent basis sets with relativistic pseudopotentials. II. Small-core pseudopotentials and correlation consistent basis sets for the post-d group 16–18 elements. J Chem Phys 119:11099–11113CrossRefGoogle Scholar
  40. 40.
    Dolg M (1996) Valence correlation energies from pseudopotential calculations. Chem Phys Lett 250:75–79CrossRefGoogle Scholar
  41. 41.
    Dolg M (1996) On the accuracy of valence correlation energies in pseudopotential calculations. J Chem Phys 104:4061–4067CrossRefGoogle Scholar
  42. 42.
    Werner HJ, Knowles PJ (1985) A second order multiconfiguration SCF procedure with optimum convergence. J Chem Phys 82:5053–5063CrossRefGoogle Scholar
  43. 43.
    Werner HJ, Meyer W (1981) Quadratically convergent MCSCF method for the simultaneous optimization of several states. J Chem Phys 74:5794–5801CrossRefGoogle Scholar
  44. 44.
    Werner HJ, Meyer W (1980) A quadratically convergent multiconfiguration–self-consistent field method with simultaneous optimization of orbitals and CI coefficients. J Chem Phys 73:2342–2356CrossRefGoogle Scholar
  45. 45.
    Werner HJ, Knowles PJ, Manby FR, Schutz M (2015) MOLPRO, version 2015.1.22, a package of ab initio programs. Available from: http://www.molpro.net

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

Personalised recommendations