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
-
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.
-
-
-
[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. 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. 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. 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. Marsh, F. D. J. Org. Chem., 1972, 37: 2966
-
[6]
6. Kroto, H. W. J. Chem. Phys., 1965, 44: 831
-
[7]
7. Okabe, H.; Mele, A. J. Chem. Phys., 1969, 51: 2100
-
[8]
8. Milligen, D. E.; Jacox, M. E.; Bass, A. M. J. Chem. Phys., 1965, 43: 3149
-
[9]
9. Milligen, D. E.; Jacox, M. E. J. Chem. Phys., 1965, 45: 1387
-
[10]
10. Schoen, L. J. J. Chem. Phys., 1965, 45: 2773
-
[11]
11. Jennings, K. R.; Linnett, J. W. Faraday Soc., 1960, 56: 1737
-
[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. Marsh, F. D.; Hermes, M. E. J. Am. Chem. Soc., 1964, 86: 4506
-
[14]
14. Jensen, J. O. J. Mol. Struct. -Theochem, 2005, 730: 235
-
[15]
15. Türker, L.; Atalar, T. J. Hazard. Mater., 2008, 153: 966
-
[16]
16. Costain, C. C.; Kroto, H. W. Can. J. Phys., 1972, 50: 1453
-
[17]
17. Almenningen, A.; Bak, B.; Jansen, P.; Strand, T. G. Acta Chim. Scand., 1973, 27: 1531
-
[18]
18. Werner, H. J.; Knowles, P. J. J. Chem. Phys., 1985, 82: 5053
-
[19]
19. Knowles, P. J.;Werner, H. J. Chem. Phys. Lett., 1985, 115: 259
-
[20]
20. Eckert, F.; Werner, H. J. Theor. Chem. Acc., 1998, 100: 21
-
[21]
21. Werner, H. J. ; Knowles, P. J. Chem. Phys., 1988, 89: 5803
-
[22]
22. Knowles, P. J.;Werner, H. J. Chem. Phys. Lett., 1988, 145: 514
-
[23]
23. Werner, H. J.; Knowles, P. J.; Lindh, R.; et al. MOLPRO, a package of ab initio programs. version 2006.1
-
[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. NIST Chemisty Webbook [DB]. LinstromP. J.; Mallard W. G. Eds. Available from: http://webbook.NIST. v/chemistry
-
[1]
-
-
-
[1]
Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
-
[2]
Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
-
[3]
Hongting Yan , Aili Feng , Rongxiu Zhu , Lei Liu , Dongju Zhang . Reexamination of the Iodine-Catalyzed Chlorination Reaction of Chlorobenzene Using Computational Chemistry Methods. University Chemistry, 2025, 40(3): 16-22. doi: 10.12461/PKU.DXHX202403010
-
[4]
Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
-
[5]
Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 133-139. doi: 10.3866/PKU.DXHX202309024
-
[6]
Jiabo Huang , Quanxin Li , Zhongyan Cao , Li Dang , Shaofei Ni . Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations. University Chemistry, 2025, 40(3): 153-159. doi: 10.12461/PKU.DXHX202405172
-
[7]
Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V2O5/TiO2 catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
-
[8]
Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, 2024, 39(3): 395-400. doi: 10.3866/PKU.DXHX202309018
-
[9]
Yong Wang , Yingying Zhao , Boshun Wan . Analysis of Organic Questions in the 37th Chinese Chemistry Olympiad (Preliminary). University Chemistry, 2024, 39(11): 406-416. doi: 10.12461/PKU.DXHX202403009
-
[10]
Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . 液相法制备硫化物固体电解质及其在全固态锂电池中的应用. Acta Physico-Chimica Sinica, 2025, 41(1): 2309019-. doi: 10.3866/PKU.WHXB202309019
-
[11]
Zihan Lin , Wanzhen Lin , Fa-Jie Chen . Electrochemical Modifications of Native Peptides. University Chemistry, 2025, 40(3): 318-327. doi: 10.12461/PKU.DXHX202406089
-
[12]
Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
-
[13]
Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039
-
[14]
Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
-
[15]
Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
-
[16]
Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
-
[17]
Jia Zhou . Constructing Potential Energy Surface of Water Molecule by Quantum Chemistry and Machine Learning: Introduction to a Comprehensive Computational Chemistry Experiment. University Chemistry, 2024, 39(3): 351-358. doi: 10.3866/PKU.DXHX202309060
-
[18]
Xiaowu Zhang , Pai Liu , Qishen Huang , Shufeng Pang , Zhiming Gao , Yunhong Zhang . Acid-Base Dissociation Equilibrium in Multiphase System: Effect of Gas. University Chemistry, 2024, 39(4): 387-394. doi: 10.3866/PKU.DXHX202310021
-
[19]
Xiaosong PU , Hangkai WU , Taohong LI , Huijuan LI , Shouqing LIU , Yuanbo HUANG , Xuemei LI . Adsorption performance and removal mechanism of Cd(Ⅱ) in water by magnesium modified carbon foam. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1537-1548. doi: 10.11862/CJIC.20240030
-
[20]
Yuejiao An , Wenxuan Liu , Yanfeng Zhang , Jianjun Zhang , Zhansheng Lu . Revealing Photoinduced Charge Transfer Mechanism of SnO2/BiOBr S-Scheme Heterostructure for CO2 Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(12): 2407021-. doi: 10.3866/PKU.WHXB202407021
-
[1]
Metrics
- PDF Downloads(1166)
- Abstract views(3482)
- HTML views(6)