Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

Ab Initio Studies on the $(HF)_2(CO)$ Trimers

$(HF)_2(CO)$ 분자착물에 관한 Ab Initio 연구

  • 발행 : 19981200
Download PDF
⟨ Previous Next ⟩

초록

The HF-SCF, MP2 and B3LYP calculations have been performed on the two conceivable clusters $(HF)_2(CO)$ trimers as well as their dimer complexes FH…FH, FH…CO and FH…OC applying $6-31+G^{\ast}^{\ast}$, and $6-311+G^{\ast}^{\ast}$ basis sets. A variety of ground state properties of these trimer complexes have been listed, and compared with corresponding properties of isolated monomers and combined dimers. It was calculated that FH…CO is more stable than FH…OC by average 0.85 kcal/mol and F-H…F-H…C≡O is more stable than F-H…F-H…O≡C by 1-2 kcal/mol. The C≡O stretching bands of the F-H…F-H…C≡O and F-H…F-H…O≡C were red shifted by 24, $37\;cm^{-1}$ compared with the FH…CO and FH…OC respectively. Also, H-F stretching bands were red shifted by 54 and $353\;cm^{-1}$.

$6-31+G^{\ast}^{\ast}와\;6-311+G^{\ast}^{\ast}$의 기본조를 사용해서 이합체 분자착물 FH…FH, FH…CO, FH…OC 뿐만 아니라 $(HF)_2(CO)$의 형성가능한 두가지 삼합체 분자착물들에 대해서 HF-SCF, MP2 그리고 B3LYP 계산을 수행했다. 이 삼합체 분자착물들에 대한 여러 가지 바닥상태 성질들을 구하였으며, 대응하는 단위체들과 이합체들의 성질들과 비교하였다. FH…CO가 FH…OC에 비해 평균 0.85 kcal/mol 만큼 안정했고, F-H…F-H…C≡O가 F-H…F-H…O≡C 보다 1∼2 kcal/mol 만큼 안정한 것으로 계산되었다. 삼합체 분자착물 형성에 따른 C≡O stretching band 는 그들의 이합체들(FH…CO, FH…OC)에 비해 각각 24, $37\;cm^{-1}$만큼, H-F stretching band는 각각 $54, 353\; cm^{-1}$만큼 red shift 되는 것으로 평가되었다.

키워드

참고문헌

  1. Chem. Phys. Lett. v.102 Karpfen, A.;Beyer, A.;Schuster, P.
  2. The Hydrogen Bond Recent Developments in Theory and Experiments v.1~3 Schuster, P.;Zundel, G.;Sandorfy, C.
  3. Angew. Chemie. Int. ED. v.20 Schuster, P.
  4. J. Am. Chem. Soc. v.99 Kollman, P.
  5. Chem. Phys. v.120 Rhee, S. K.;Karpfen, A.
  6. Structure and Dynamics of Weakly Bound complexes Botchwina, P.;Weber, A.(Ed.)
  7. Topics Current Chem. v.120 Beyer, A.;Karpfen A.;Schuster, P.
  8. J. Chem. Phys. v.101 LatajKa, Z.;Bouteiller, Y.
  9. Theorectical Models of Chemical Bonding Scheiner, S.;Maksic, Z. B.(Ed.)
  10. Review in Computational Chemistry Scheiner, S.;Lipkowitz, K.;Boyd, D.(Ed.)
  11. Trends Chem. Phys. v.1 Bouteiller, Y.
  12. J. Phys. Chem. v.97 Rasine, S. C.;Davidson, E. R.
  13. J. Chem. Phys. v.96 Andzelm J.;Wimmer, E.
  14. J. Chem. Phys. v.97 Johnson, B. G.;Gill, P. M. W.;Pole, J. A.
  15. Topics on Current Chemistry v.120 A. Bayer;A. Karpfen;Schuster, P.
  16. Acta Crystallor Atoji, M.;Lipscomb, W. N.
  17. J. Chem. Phys. v.55 Del Bene, J.
  18. Modern Theoretical Chemistry v.3 Basis sets for Molecular Calculations Dunning, T. H.;Hay, P. J.
  19. Applications of Electronic Structure Theory v.3 Schaefer, H. F. III(ed.)
  20. J. Chem. Phys. v.52 Hankins, D.;Moskowitz, J. W.;Stillinger F. H.
  21. Theor. Chim. Acta. Diercksen, G. H. F.
  22. J. Phys. Chem. v.93 Schatte, G. H.;Hoge, D. W.;Knozinger, E.;Schrems, O.
  23. The Theory of Rotating Diatomic Molecules Mizushima, M.
  24. Spectra of Diatomic Molecules Herzberg, G.
  25. J. Chem. Phys. v.81 Michael, D. W.;Dykstra, C. E.;Lisy, J. M.
  26. J. Chem. Phys. v.88 Hancock, G. C.;Truhlar, D. G.;Dykstra, C. E.
  27. Natl. Stand. Ref. Data. Ser., Natl. Bur. Stand. No. 10 Selected Values of Electric Dipole moments for Molecules in the Gas Phase Nelson, R. D.;Lide, D. R.;Maryott, A. A.
  28. J. Chem. Phys. v.30 Burrus, C. A.
  29. Molecular Spectra and Molecular Structure, IV. Constants of Diatomic Molecules Huber, K. P.;Herzberg, G.