Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Theoretical Studies of the Low-Lying Electronic States of Diazirine and 3,$3^{\prime} $-Dimenthyldiazirine

  • Published : 1999.11.20
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Abstract

The low-lying electronic states of diazirine and 3,3'-dimethyldiazirine have been studied by high level ab initio quantum chemical methods. The equilibrium geometries of the ground state and the first excited singlet and triplet states have been optimized using the Hartree-Fock (HF) and complete active space SCF (CASSCF) methods, as well as using the Møller-Plesset second order perturbation (MP2) theory and the single configuration interaction (CIS) theory. It was found that the first excited singlet state is of 1 B1 symmetry resulting from the n- π* transition, while the first excited triplet state is of 3 B2 symmetry resulting from the π- π* transition. The harmonic vibrational frequencies have been calculated at the optimized geometry of each electronic state, and the scaled frequencies have been compared with the experimental frequencies available. The adiabatic and vertical transition energies from the ground electronic state to the low-lying electronic states have been estimated by means of multireference methods based on the CASSCF wavefunctions, i.e., the multiconfigurational quasidegenerate second order perturbation (MCQDPT2) theory and the CASSCF second-order configuration interaction (CASSCF-SOCI) theory. The vertical transition energies have also been calculated by the CIS method for comparison. The computed transition energies, particularly by MCQDPT2, agree well with the experimental observations, and the electronic structures of the molecules have been discussed, particularly in light of the controversy over the existence of the so-called second electronic state.

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References

  1. J. Am. Chem. Soc. v.84 Graham, W. H.
  2. Tetrahedron Lett. Schmitz, E.;Ohme, R.
  3. Chem. ber. v.95 Schmitz, E.;Ohme, R.
  4. J. Am. Chem. Soc. v.84 Pierce, L.;Dobyns, V.
  5. J. Chem. Phys. v.49 Wollrab, J. E.;Scharpen, L. H.;Ames, D. P.;Merritt, J. A.
  6. J. Chem. Phys. v.50 Scharpen, L. H.;Wollrab, J. E.;Ames, D. P.Merritt, J. A.
  7. J. Am. Chem. Soc. v.89 Hencher, J. L.;Bauer, S. H.
  8. J. Chem. Phys. v.40 Ettinger, R.
  9. J. Mol. Spectrosc. v.27 Mitchell, R. W.;Merritt, J. A.
  10. J. Mol. Spectrosc. v.29 Mitchell, R. W.;Merritt, J. A.
  11. Can. J. Phys. v.40 Merritt, J. A.
  12. J. Mol. Spectrosc. v.19 Robertson, L. C.;Merritt, J. A.
  13. J. Mol. Spectrosc. v.22 Mitchell, R. W.;Merritt, J. A.
  14. J. Mol. Spectrosc. v.24 Robertson, L. C.;Merritt, J. A.
  15. J. Chem. Phys. v.56 Robertson, L. C.;Merritt, J. A.
  16. J. Chem. Phys. v.57 Robertson, L. C.;Merritt, J. A.
  17. J. Mol. Spectrosc. v.17 Simmons, J. D.;Bartky, I. R.;Bass, A. M.
  18. J. Chem. Phys. v.51 Lombardi, J. R.;Klemperer, W.;Robin, M. B.;Basch, H.;Kuebler, N. A.
  19. J. Chem. Phys. v.51 Robin, M. B.;Basch, H.;Kuebler, N. A.;Wiberg, K. B.;Ellison, G. B.
  20. J. Mol. Spectrosc. v.50 Hepburn, P. H.;Hollas, J. M.
  21. J. Am. Chem. Soc. v.114 Modarelli, D. A.;Morgan, S.;Platz, M. S.
  22. J. Am. Chem. Soc. v.120 Ford, F.;Yuzawa, T.;Platz, M. S.;Matzinger, S.;Fulscher, M.
  23. J. Am. Chem. Soc. v.115 Modarelli, D. A.;Platz, M. S.
  24. J. Photochem. Photobiol. A v.108 Kim, T.-S.;Choi, Y. S.;Kwak, I.
  25. Ph.D. Dissertation, Inha University Kim, T.-S.
  26. J. Chem. Phys. v.107 Kim, T.-S.;Kim, S. K.;Choi, Y. S.;Kwak, I.
  27. Chem. Phys. v.15 Vasuvedan, K.;Kammer, W. E.
  28. J. Am. Chem. Soc. v.100 Bigot, B.;Ponec, R.;Sevin, A.;Devaquet, A.
  29. J. Am. Chem. Soc. v.107 Muller-Rammers, P. L.;Jug, K.
  30. J. Am. Chem. Soc. v.116 Yamamoto, N.;Bernardi, F.;Bottoni, A.;Olivucci, M.;Robb, M. A.;Wilsey, S.
  31. Ab Initio Methods in Quantum Chemistry-Ⅱ Lawley, K. P.(Ed.)
  32. Chem. Phys. Lett. v.207 Nakano, H.
  33. J. Chem. Phys. v.99 Nakano, H.
  34. Ph.D. Thesis, Stanford University Schaefer, H. F.
  35. J. Comput. Chem. v.14 Schmidt, M. W.;Baldridge, K. K.;Boatz, J. A.;Elbert, S. T.;Gordon, M. S.;Jensen, J. H.;Koseki, S.;Matsunaga, N.;Nguyen, K. A.;Su, S. J.;Windus, T. L.;Dupuis, M.;Montgomery, J. A.
  36. Gaussian 94, Revision E.2 Frisch, M. J.;Trucks, G. W.;Schlegel, H. B.;Gill, P. M. W.;Johnson, B. G.;Robb, M. A.;Cheeseman, J. R.;Keith, T.;Petersson, G. A.;Montgomery, J. A.;Raghavachari, K.;Al-Laham, M. A.;Zakrzewski, V. G.;Ortiz, J. V.;Foresman, J. B.;Cioslowski, J.;Stefanov, B. B.;Nanayakkara, A.;Challacombe, M.;Peng, C. Y.;Ayala, P. Y.;Chen, W.;Wong, M. W.;Andres,J. L.;Replogle, E. S.;Gomperts, R.;Martin, R. L.;Fox, D. J.;Binkley, J. S.;Defress, D. J.;Baker, J.;Stewart, J. P.;Head-Gordon, M.;Gonzalez, C.;Pople, J. A.
  37. Int. J. Quantum Chem. Symp. v.S15 Pople, J. A.;Schlegel, H. B.;Krishnan, R.;DeFrees, D. J.;Binkley, J. S.;Frisch, M. J.;Whiteside, R. A.;Hout, R. F.;Hehre, W. J.
  38. J. Comput. Chem. v.3 Hout, R. F.;Levi, B. A.;Hehre, W. J.
  39. Isr. J. Chem. v.33 Pople, J. A.;Scott, A. P.;Wong, M. W.;Radom, L.
  40. J. Phys. Chem. v.100 Scott, A. P.;Radom, L.
  41. J. Phys. Chem. v.96 Foresman, J. B.;Head-Gordon, M.;Pople, J. A.;Frisch, M. J.
  42. Chem. Phys. Lett. v.192 Roos, B. O.;Andersson, K.;Fulscher, M. P.