Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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PMO Theory of Orbital Interaction (Ⅴ). ${\pi}$-${\pi}$ and ${\pi}^{\ast}$-${\pi}^{\ast}$ Orbital Interactions

궤도간 상호작용의 PMO 이론 (제5보). ${\pi}$-${\pi}$ 및 ${\pi}^{\ast}$-${\pi}^{\ast}$ 궤도간 상호작용

  • Ik Choon Lee (Department of Chemistry, Inha University) ;
  • Ki Yull Yang (Department of Chemistry, Inha University) ;
  • Nan Pyo Lee (Department of Chemistry, Inha University) ;
  • Wang Ki Kim (Department of Chemical Education, Chonnam National University)
  • 이익춘 (인하대학교 이과대학 화학과) ;
  • 양기열 (인하대학교 이과대학 화학과) ;
  • 이난표 (인하대학교 이과대학 화학과) ;
  • 김왕기 (전남대학교 사범대학 화학교육과)
  • Published : 1985.02.20
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Abstract

PMO expressions for ${\pi}^{\ast}$-${\pi}^{\ast}$ orbital interaction have been derived. Important differences between ${\pi}$-${\pi}$ and ${\pi}^{\ast}$-${\pi}^{\ast}$ interactions predicted by PMO expressions are : (ⅰ) energy splitting in ${\pi}^{\ast}$-${\pi}^{\ast}$ interaction will be greater than that in ${\pi}$-${\pi}$ interaction, (ⅱ) energy change due to interaction will be more destabilizing in ${\pi}^{\ast}$-${\pi}^{\ast}$ than in ${\pi}$-${\pi}$ interaction. These predictions were borne out in experimental data and in results of MO theoretical computations. It was pointed out that both STeO-3G and INDO-LCBO methods underestimate ${\pi}^{\ast}$-${\pi}^{\ast}$ orbital interaction and in order to estimate properly with MO theoretical calculation, use of split valence basis set is required.

${\pi}^{\ast}$-${\pi}^{\ast}$ 궤도간 상호작용에 관한 섭동식을 유도하였다. 섭동식으로부터 예측되는 ${\pi}$-${\pi}$와 ${\pi}^{\ast}$-${\pi}^{\ast}$ 상호작용간의 중요한 두가지 차이점은 : (ⅰ)에너지분리정도가 ${\pi}$-${\pi}$ 상호작용의 경우보다 ${\pi}^{\ast}$-${\pi}^{\ast}$의 경우가 더 컸으며, ( ii ) 상호작용에 의한 에너지 변화량은 ${\pi}$-${\pi}$ 상호작용의 경우보다 ${\pi}^{\ast}$-${\pi}^{\ast}$의 경우가 더 불안정화 되었다. 이러한 예측들은 실험결과들과 MO이론적 계산에 의하여 잘 밝혀졌다. 한편 STO-3G 및 INDO-LCBO 계산방법은 ${\pi}^{\ast}$-${\pi}^{\ast}$ 상호작용을 과소평가하고 있음을 알았으며 MO이론적 계산을 이용하여 이러한 ${\pi}^{\ast}$-${\pi}^{\ast}$상호작용을 적절히 표현하는 데는 split valence 기초함수를 사용하여야 함을 밝혔다.

Keywords

References

  1. J. Amer. Chem. Soc. v.90 R. Hoffmann;A. Imamura;W. J. Hehre
  2. Bull. Chem. Soc. Japan v.51 M. Ohsaku;A. Imamura;K. Hirao
  3. Tetrahedron lett. P. Bischof;J. A. Hashmal;E. Heilbronner;V. Hornung
  4. J. Amer. Chem. Soc. v.103 R. W. Alder;R. -J. Arrowsmith;A. Casson;R. B. Sessions;E. Heilbronner;B. Kovac;H. Huber;M. Taagepera
  5. Helv. Chem. Acta v.56 F. Brogli;W. Eberbach;E. Haselbach;E. Heilbronner;V. Hornung;D. M. Lemal
  6. Tetrahedron v.37 J. W. Verhoven;P. Pasman
  7. J. Amer. Chem. Soc. v.103 M. N. Paddon-Row;H. K. Patney;R. S. Brown;K. N. Houk
  8. J. Phys. Rev. A v.5 L. Sanche;G. Schulz
  9. J. Amer. Chem. Soc. v.102 M. N. Paddon-Row;R. Hartcher
  10. J. Amer. Chem. Soc. v.102 M. N. Paddon-Row;R. Hartcher
  11. Acc. Chem. Res. v.11 K. D. Jordan;P. D. Burrow
  12. J. Phys. Chem. v.86 D. J. Pasto;D.-M. Chlpman;N.-Z. Huang
  13. J. Amer. Chem. Soc. v.104 V. Balaji;K. D. Jordan;P. D. Burrow;M. N. Paddon-Row;H. K. Patney
  14. Acc. Chem. Res. v.15 M. N. Paddon-Row
  15. J. Chem. Soc., Chem. Commun. M. N. Paddon-Row;R. Hartcher;R. N. Warrener
  16. Aust. J. Chem. v.33 M. N. Paddon-Row;R. Hartcher
  17. Tetrahedron v.39 I. Lee
  18. Bull. Korean Chem. Soc. v.3 I. Lee
  19. Bull. Inst. Basic Sci. Inha Univ. v.4 I. Lee
  20. Bull. Korean Chem. Soc. v.5 I. Lee;K. Yang
  21. J. Amer. Chem. Soc. v.104 P. D. Burrow;K. D. Jordan
  22. Angew. Chem. Internat. Edit. v.13 R. Gleiter
  23. Experimentia v.13 C. A. Grob
  24. Angew. Chem. v.79 C. A. Grob;P. W. Schiess
  25. Angew. Chem. Internat. Edit. v.6 C. A. Grob;P. W. Schiess
  26. J. Amer. Chem. Soc. v.102 J. C. Giordan;M. R. McMillan;J. H. Moore;S. W. Staley
  27. Physica v.1 T. Koopman
  28. J. Amer. Chem. Soc. v.103 S. W. Staley;M. D. Bjorke;J. C. Giordan;M. R. McMillan;J. H. Moore.
  29. J. Chem. Phys. v.51 W. J. Hehre;R. F. Stewart;J. A. Pople
  30. J. Chem. Phys. v.54 R. Ditchfield;W. J. Hehre;J. A. Pople
  31. J. Amer. Chem. Soc. v.98 F. Weinhold;T. K. Brunck
  32. J. Amer. Chem. Soc. v.101 T. K. Brunck;F. Weinhold
  33. J. Amer. Chem. Soc. v.105 K. Raghavachari;R. C. Haddon;H. D. Roth
  34. J. Amer. Chem. Soc. v.97 R. C. Bingham;M. J. S. Dewar;D. H. Lo
  35. J. Electron Spectrosc. v.4 N. Border;B. H. Chen;S. D. Worley
  36. J. Chem. Phys. v.71 D. M. Minz;A. Kuppermann
  37. Helv. Chim. Acta. v.52 P. Bischof;J. A. Harshmall;E. Heilbronner;V. Hornung
  38. Chem. Ber. v.106 R. Gleiter;E. Heilbronner;M. Hekman;H.-D. Martin
  39. Chem. Ber. v.107 H.-D. Martin;R. Schwesinger
  40. Angew. Chem. Internat. Edit. v.16 H. Prinzbach;G. Sedelmeir;H.-D. Martin