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Volumn 111, Issue 5, 2007, Pages 971-975

Model study on the pyridine - Dewar pyridine and some related photoisomerization reactions

Author keywords

[No Author keywords available]

Indexed keywords

ARSABENZENE; GROUND-STATE REACTIONS; PHOTOISOMERIZATION; PYRIDINE;

EID: 33847066327     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp064928a     Document Type: Article
Times cited : (17)

References (33)
  • 16
    • 33847063421 scopus 로고    scopus 로고
    • A recent study of femtosecond dynamics as well as theoretical calculations of pyridine by Zewail and Chachisvilis explored the photochemical dynamics of the S2(π, π*) excited state leading to the formation of the azaprefulvene isomer. Also, they found that the reaction path on the S2(π, π*) potential energy surface was the lowest path for the formation of the azaprefulvene isomer at the CASSCF level. See ref 2e. We are therefore confident that a pyridine species with biradical character, originating from the excited state S2π, π*, should be a precursor in the interversion of the pyridine
    • 2(π - π*), should be a precursor in the interversion of the pyridine.
  • 23
    • 33847071159 scopus 로고    scopus 로고
    • For more details, see ref, 6c and references therein
    • (b) For more details, see ref. (6c) and references therein.
  • 24
    • 33847026776 scopus 로고    scopus 로고
    • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Zakrzewski, V. G, Montgomery, J. A, Jr, Stratmann, R. E, Burant, J. C, Dapprich, S, Millam, J. M, Daniels, A. D, Kudin, K. N, Strain, M. C, Farkas, O, Tomasi, J, Barone, V, Cossi, M, Cammi, R, Mennucci, B, Pomelli, C, Adamo, C, Clifford, S, Ochterski, J, Petersson, G. A, Ayala, P. Y, Cui, Q, Morokuma, K, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Cioslowski, J, Ortiz, J. V, Baboul, A. G, Stefanov, B. B, Liu, Liashenko, G, Piskorz, A, Komaromi, P, I, Gomperts, R, Martin, R. L, Fox, D. J, Keith, T, Al-Laham, M. A, Peng, C. Y, Nanayakkara, A, Gonzalez, C, Challacombe, M, Gill, P. M. W, Johnson, B, Chen, W, Wong, M. W, Andres, J. L, Gonzalez, C, Head-Gordon, M, Replogle, E. S, Pople, J. A. Gaussian, Inc, Pittsburgh, PA, 2003
    • Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, Liashenko, G.; Piskorz, A.; Komaromi, P.; I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian, Inc.: Pittsburgh, PA, 2003.
  • 27
    • 33847012936 scopus 로고    scopus 로고
    • According to the results outlined in Figure 2, funneling through 82/80 CI (i.e., CI-A and CI-B) leads to two different reaction paths on the ground-state surface, via either the derivative coupling vector or the gradient difference vector. For instance, the gradient difference vector for CI-A corresponds to an antisymmetric bending motion, which may lead to a vibrationally hot species at the So configuration. On the other hand, its derivative coupling vector corresponds to the intramolecular formation of a Dewar pyridine, 2. Besides these, again, the derivative coupling vector for Cl-B can lead to the isomer 3, whereas its gradient difference vector may result in a vibrationally hot species at the So configuration.
    • According to the results outlined in Figure 2, funneling through 82/80 CI (i.e., CI-A and CI-B) leads to two different reaction paths on the ground-state surface, via either the derivative coupling vector or the gradient difference vector. For instance, the gradient difference vector for CI-A corresponds to an antisymmetric bending motion, which may lead to a vibrationally hot species at the So configuration. On the other hand, its derivative coupling vector corresponds to the intramolecular formation of a Dewar pyridine, 2. Besides these, again, the derivative coupling vector for Cl-B can lead to the isomer 3, whereas its gradient difference vector may result in a vibrationally hot species at the So configuration.
  • 28
    • 33847082429 scopus 로고    scopus 로고
    • 2/ So CI (i.e., CI-C and CI-D) leads to two different reaction paths on the ground-state surface, via either the derivative coupling vector or the gradient difference vector. For example, the gradient difference vector for CI-C can lead to a vibrationally hot species at the So configuration, whereas its derivative coupling vector can result in an isomer, 5. Likewise, the same situation can also be found in the left-hand side of Figure 4; that is, the gradient difference vector for CI-D can result in a vibrationally hot species at the So configuration, and its derivative coupling vector can lead to an isomer, 6.
    • 2/ So CI (i.e., CI-C and CI-D) leads to two different reaction paths on the ground-state surface, via either the derivative coupling vector or the gradient difference vector. For example, the gradient difference vector for CI-C can lead to a vibrationally hot species at the So configuration, whereas its derivative coupling vector can result in an isomer, 5. Likewise, the same situation can also be found in the left-hand side of Figure 4; that is, the gradient difference vector for CI-D can result in a vibrationally hot species at the So configuration, and its derivative coupling vector can lead to an isomer, 6.
  • 30
    • 33847023423 scopus 로고    scopus 로고
    • 0 CI (i.e., CI-E and CI-F) leads to two different reaction paths on the ground-state surface, via either the derivative coupling vector or the gradient difference vector. The derivative coupling vector for CI-E can lead to a vibrationally hot species at the So configuration. However, its gradient difference vector can result in a Dewar isomer, 8. Similarly, the gradient difference vector for CI-F can lead to vibrationally hot species at the So configuration, and its derivative coupling vector can lead to an isomer, 9.
    • 0 CI (i.e., CI-E and CI-F) leads to two different reaction paths on the ground-state surface, via either the derivative coupling vector or the gradient difference vector. The derivative coupling vector for CI-E can lead to a vibrationally hot species at the So configuration. However, its gradient difference vector can result in a Dewar isomer, 8. Similarly, the gradient difference vector for CI-F can lead to vibrationally hot species at the So configuration, and its derivative coupling vector can lead to an isomer, 9.
  • 31
    • 0004200260 scopus 로고    scopus 로고
    • 6th ed, Thomson: New York
    • Mcmurry, J. In Organic Chemistry, 6th ed.; Thomson: New York, 2004; pp 895-896.
    • (2004) Organic Chemistry , pp. 895-896
    • Mcmurry, J.1
  • 32
    • 33847045914 scopus 로고    scopus 로고
    • Unpublished results
    • Su, M.-D. Unpublished results.
    • Su, M.-D.1
  • 33
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    • For more details, see
    • For more details, see: Su, M.-D. J. Phys. Chem. 1996, 100, 4339.
    • (1996) J. Phys. Chem , vol.100 , pp. 4339
    • Su, M.-D.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.