Citation: CI Cheng-Gang, DUAN Xue-Mei, LIU Jing-Yao, SUN Chia-Chung. Photodissociation Mechanism of Cyanogen Azide[J]. Acta Physico-Chimica Sinica, ;2010, 26(10): 2787-2792. doi: 10.3866/PKU.WHXB20100914 shu

Photodissociation Mechanism of Cyanogen Azide

  • Received Date: 4 May 2010
    Available Online: 27 September 2010

    Fund Project: 国家自然科学基金(20333050, 20303007, 20973077) 和教育部新世纪优秀人才支持计划(NCET) 资助项目 (20333050, 20303007, 20973077) 和教育部新世纪优秀人才支持计划(NCET)

  • We investigated the photodissociation mechanism of cyanogen azide (N3CN) at the MRCI+Q//CAS(10,9)/6-311+G(2df) level of theory using the multi-reference state method. The optimized structures and energies of the minima, transition states, singlet/singlet conical intersection and singlet/triplet crossing points of the ground and low-lying excited states were obtained to explore the potential energy surfaces of N3CN. The vertical excited energies calculated at the MRCI+Q//CAS(10, 9) level were compared with the experimental data. It is shown that N—N bond fission to form N2+NCN is the predominant dissociation pathway on the S0, S1, S2, and T1 surfaces whereas the C—N bond fission channel is the minor pathway. The 220 nm absorption peak observed experimentally corresponds to an excitation from the S0 to the S1 state leading to the major photodissociation product NCN[a1Δg]. The 275 nm absorption peak corresponds to the S0-T1 transition leading to the formed ground-state product NCN[X3Σ-g ] via the barrierlessly direct dissociation in the T1 state. Our theoretical results agree well with experimental observations.

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    1. [1]

      1. Xiao, H. M.; Li, Y. F.; Qian, J. J. Acta Phys. -Chim. Sin., 1994, 10 (3): 235 [肖鹤鸣, 李永富,钱建军.物理化学学报, 1994, 10(3): 235]

    2. [2]

      2. Xu, W. Y.; Liu, G. S.; Peng, Y. Y.; Hong, S. G. Acta Phys. -Chim. Sin., 1998, 14(7): 669 [徐文渊,刘够生,彭以元, 洪三国.物理 化学学报, 1998, 14(7): 669]

    3. [3]

      3. Li, J. S.; Xiao, H. M. Acta Phys. -Chim. Sin., 2000, 16(1): 36 [李金山,肖鹤鸣.物理化学学报, 2000, 16(1): 36]

    4. [4]

      4. Javad, H.; Naader, A.; Soraia, M.; Mehdi, A. Acta Phys. -Chim. Sin., 2009, 25(6): 1239 [Javad, H.; Naader, A.; Soraia, M.; Mehdi, A.物理化学学报, 2009, 25(6): 1239]

    5. [5]

      5. Marsh, F. D. J. Org. Chem., 1972, 37: 2966

    6. [6]

      6. Kroto, H. W. J. Chem. Phys., 1965, 44: 831

    7. [7]

      7. Okabe, H.; Mele, A. J. Chem. Phys., 1969, 51: 2100

    8. [8]

      8. Milligen, D. E.; Jacox, M. E.; Bass, A. M. J. Chem. Phys., 1965, 43: 3149

    9. [9]

      9. Milligen, D. E.; Jacox, M. E. J. Chem. Phys., 1965, 45: 1387

    10. [10]

      10. Schoen, L. J. J. Chem. Phys., 1965, 45: 2773

    11. [11]

      11. Jennings, K. R.; Linnett, J. W. Faraday Soc., 1960, 56: 1737

    12. [12]

      12. Benard, D. J.; Linnen, C.; Harker, A.; Michels, H. H.; Addision, J. B.; Ondercin, R. J. Phys. Chem. B, 1998, 102: 6010

    13. [13]

      13. Marsh, F. D.; Hermes, M. E. J. Am. Chem. Soc., 1964, 86: 4506

    14. [14]

      14. Jensen, J. O. J. Mol. Struct. -Theochem, 2005, 730: 235

    15. [15]

      15. Türker, L.; Atalar, T. J. Hazard. Mater., 2008, 153: 966

    16. [16]

      16. Costain, C. C.; Kroto, H. W. Can. J. Phys., 1972, 50: 1453

    17. [17]

      17. Almenningen, A.; Bak, B.; Jansen, P.; Strand, T. G. Acta Chim. Scand., 1973, 27: 1531

    18. [18]

      18. Werner, H. J.; Knowles, P. J. J. Chem. Phys., 1985, 82: 5053

    19. [19]

      19. Knowles, P. J.;Werner, H. J. Chem. Phys. Lett., 1985, 115: 259

    20. [20]

      20. Eckert, F.; Werner, H. J. Theor. Chem. Acc., 1998, 100: 21

    21. [21]

      21. Werner, H. J. ; Knowles, P. J. Chem. Phys., 1988, 89: 5803

    22. [22]

      22. Knowles, P. J.;Werner, H. J. Chem. Phys. Lett., 1988, 145: 514

    23. [23]

      23. Werner, H. J.; Knowles, P. J.; Lindh, R.; et al. MOLPRO, a package of ab initio programs. version 2006.1

    24. [24]

      24. Butler, G. B.; Berlin, K. D. Foundation of organic chemistry (theory and application). Trans. Zhang, L. P.; Tu, Y. R. Beijing: People Education Press, 1980: 501 [Butler, G. B.; Berlin, K. D. 有机化学基础(理论和应用). 张丽蘋, 涂余如,译. 北京: 人民教 育出版社, 1980: 501]

    25. [25]

      25. NIST Chemisty Webbook [DB]. LinstromP. J.; Mallard W. G. Eds. Available from: http://webbook.NIST. v/chemistry


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