邻二氯苯激发态动力学

引用本文: 李晓营, 王利, 王艳秋, 宋哲, 刘本康. 邻二氯苯激发态动力学[J]. 物理化学学报, 2015, 31(9): 1655-1661. doi: 10.3866/PKU.WHXB201506291 shu

Citation: LI Xiao-Ying, WANG Li, WANG Yan-Qiu, SONG Zhe, LIU Ben-Kang. Dynamics of Excited o-Dichlorobenzene[J]. Acta Physico-Chimica Sinica, 2015, 31(9): 1655-1661. doi: 10.3866/PKU.WHXB201506291 shu

邻二氯苯激发态动力学

李晓营 ^1, ,
王利 ^2, ,
王艳秋 ^3, ,
宋哲 ^1, ,
刘本康 ^3,

基金项目:
国家自然科学基金(21303199)资助项目 (21303199)

摘要:

利用飞秒分辨的激光泵浦-探测技术结合飞行时间质谱和光电子速度成像方法研究了邻二氯苯第一电子单重激发态(S₁)的超快动力学. 邻二氯苯的S₁态振动基态寿命为(651 ± 10) ps, 对应于S₁振动基态向三重态的系间窜越过程. 邻二氯苯S₁的高振动激发9a₂18a₂对应两个衰减通道, 其中寿命为(458 ± 12) fs的超快过程对应于由处于振动激发的S₁向高振动激发的基态(S₀)发生的内转换过程, 而寿命为(90 ± 10) ps过程则对应由S₁态向三重态(T₁)的系间窜越过程, 电离产生的光电子能谱中长寿命的谱峰可能与系间窜越过程有关. S₁态高振动态的旋轨耦合程度比低振动态的更强, 导致系间窜越过程更快.

关键词:

English

Dynamics of Excited o-Dichlorobenzene

1.
1 School of Physics and Electronic Technology, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China;
2 College of Physics and Materials Engineering, Dalian Nationalities University, Dalian 116600, Liaoning Province, P. R. China;
3 State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, P. R. China
Received Date: 07 April 2015
Available Online: 06 September 2015
Fund Project:
国家自然科学基金(21303199)资助项目

Abstract:

The dynamics of the first excited singlet electronic state (S₁) of o-dichlorobenzene was investigated in real time by the femtosecond pump-probe method combined with time-of-flight mass spectroscopy and the photoelectron velocity mapping technique. The lifetime of the S₁ vibrational ground state was determined experimentally to be (651 ± 10) ps, corresponding to the intersystem crossing process from the S₁ state to the triplet state. Two decay channels were found in the S₁ vibrationally excited mode 9a₂18a₂. The fast process (lifetime constant (458 ± 12) fs) is because of the internal conversion from the S₁ vibrationally excited mode to the highly vibrationally excited ground state (S₀). The slow process (lifetime constant (90 ± 10) ps) is attributed to the intersystem crossing process from the S₁ state to the triplet state (T₁). Photoelectrons with long lifetime characteristics in the spectrum might be connected with the intersystem crossing process. Enhanced spinorbital coupling in the S₁ highly vibrationally excited state accelerates the intersystem crossing process.

Key words:

1. [1]
  
  (1) Zewail, A. H. Angew. Chem. Intl. Edit. Engl. 2000, 39, 2586.
  (1) Zewail, A. H. Angew. Chem. Intl. Edit. Engl. 2000, 39, 2586.
2. [2]
  (2) Hertel, I. V.; Radloff, W. Rep. Prog. Phys. 2006, 69, 1897. doi: 10.1088/0034-4885/69/6/R06(2) Hertel, I. V.; Radloff, W. Rep. Prog. Phys. 2006, 69, 1897. doi: 10.1088/0034-4885/69/6/R06
3. [3]
  (3) Gullett, B.; Oudejans, L.; Touati, A.; Ryan, S.; Tabor, D. J. Mater. Cycles Waste Manage. 2008, 10, 32. doi: 10.1007/s10163-007-0195-8(3) Gullett, B.; Oudejans, L.; Touati, A.; Ryan, S.; Tabor, D. J. Mater. Cycles Waste Manage. 2008, 10, 32. doi: 10.1007/s10163-007-0195-8
4. [4]
  (4) Gaber, A.; Riese, M.; Grotemeyer, J. J. Phys. Chem. A 2008, 112, 425. doi: 10.1021/jp074802t(4) Gaber, A.; Riese, M.; Grotemeyer, J. J. Phys. Chem. A 2008, 112, 425. doi: 10.1021/jp074802t
5. [5]
  (5) Gaber, A.; Riese, M.; Witte, F.; Grotemeyer, J. Phys. Chem. Chem. Phys. 2009, 11, 1628. doi: 10.1039/b816800h(5) Gaber, A.; Riese, M.; Witte, F.; Grotemeyer, J. Phys. Chem. Chem. Phys. 2009, 11, 1628. doi: 10.1039/b816800h
6. [6]
  (6) Fujisawa, S.; Oonishi, I.; Masuda, S.; Ohno, K.; Harada, Y. J. Phys. Chem. 1991, 95, 4250. doi: 10.1021/j100164a017(6) Fujisawa, S.; Oonishi, I.; Masuda, S.; Ohno, K.; Harada, Y. J. Phys. Chem. 1991, 95, 4250. doi: 10.1021/j100164a017
7. [7]
  (7) Scharping, H.; Zetzsch, C. J. Mol. Spectrosc. 1995, 112, 8. doi: 10.1016/0022-2852(85)90186-9(7) Scharping, H.; Zetzsch, C. J. Mol. Spectrosc. 1995, 112, 8. doi: 10.1016/0022-2852(85)90186-9
8. [8]
  (8) Weichhardt, C.; Zimmermann, R.; Schramm, K. W.; Boesl, U.; Schlag, E. W. Rapid Commun. Mass Spectrom. 1994, 8, 381.(8) Weichhardt, C.; Zimmermann, R.; Schramm, K. W.; Boesl, U.; Schlag, E. W. Rapid Commun. Mass Spectrom. 1994, 8, 381.
9. [9]
  (9) Imura, K.; Kishimoto, N.; Ohno, K. J. Phys. Chem. A 2001, 105, 9111. doi: 10.1021/jp011970r(9) Imura, K.; Kishimoto, N.; Ohno, K. J. Phys. Chem. A 2001, 105, 9111. doi: 10.1021/jp011970r
10. [10]
  (10) Singh, I. B.; Rai, S. B.; Rai, D. K. J. Mol. Spectrosc. 1994, 163, 364. doi: 10.1006/jmsp.1994.1032(10) Singh, I. B.; Rai, S. B.; Rai, D. K. J. Mol. Spectrosc. 1994, 163, 364. doi: 10.1006/jmsp.1994.1032
11. [11]
  (11) Borg, O. A.; Karlsson, D.; Isomaki-Krondahl, M.; Davidsson, J.; Lunell, S. Chem. Phys. Lett. 2008, 456, 123. doi: 10.1016/j.cplett.2008.03.030(11) Borg, O. A.; Karlsson, D.; Isomaki-Krondahl, M.; Davidsson, J.; Lunell, S. Chem. Phys. Lett. 2008, 456, 123. doi: 10.1016/j.cplett.2008.03.030
12. [12]
  (12) Potts, A. W.; Holland, D. M. P.; Powis, I.; Karlsson, L.; Trofimov, A. B.; Bodzuk, I. L. Chem. Phys. 2013, 415, 84. doi: 10.1016/j.chemphys.2012.12.031(12) Potts, A. W.; Holland, D. M. P.; Powis, I.; Karlsson, L.; Trofimov, A. B.; Bodzuk, I. L. Chem. Phys. 2013, 415, 84. doi: 10.1016/j.chemphys.2012.12.031
13. [13]
  (13) Powis, I.; Trofimov, A. B.; Bodzuk, I. L.; Holland, D. M. P.; Potts, A. W.; Karlsson, L. Chem. Phys. 2013, 415, 291. doi: 10.1016/j.chemphys.2012.09.026(13) Powis, I.; Trofimov, A. B.; Bodzuk, I. L.; Holland, D. M. P.; Potts, A. W.; Karlsson, L. Chem. Phys. 2013, 415, 291. doi: 10.1016/j.chemphys.2012.09.026
14. [14]
  (14) Shimoda, A.; Hikida, T.; Morl, Y. J. Phys. Chem. 1979, 83, 1309. doi: 10.1021/j100473a015(14) Shimoda, A.; Hikida, T.; Morl, Y. J. Phys. Chem. 1979, 83, 1309. doi: 10.1021/j100473a015
15. [15]
  (15) Han, K. L.; He, G. Z. J. Photochem. Photobiol. C-Photochem. Rev. 2007, 8, 55. doi: 10.1016/j.jphotochemrev.2007.03.002(15) Han, K. L.; He, G. Z. J. Photochem. Photobiol. C-Photochem. Rev. 2007, 8, 55. doi: 10.1016/j.jphotochemrev.2007.03.002
16. [16]
  (16) Liu, B. K.; Wang, B. X.; Wang, Y. Q.; Wang, L. Chem. Phys. Lett. 2009, 477, 266. doi: 10.1016/j.cplett.2009.07.025(16) Liu, B. K.; Wang, B. X.; Wang, Y. Q.; Wang, L. Chem. Phys. Lett. 2009, 477, 266. doi: 10.1016/j.cplett.2009.07.025
17. [17]
  (17) Liu, Y. J.; Persson, P.; Lunell, S. J. Chem. Phys. 2004, 121, 11000. doi: 10.1063/1.1810135(17) Liu, Y. J.; Persson, P.; Lunell, S. J. Chem. Phys. 2004, 121, 11000. doi: 10.1063/1.1810135
18. [18]
  (18) Sponer, H. Rev. Mod. Phys. 1942, 14, 224. doi: 10.1103/RevModPhys.14.224(18) Sponer, H. Rev. Mod. Phys. 1942, 14, 224. doi: 10.1103/RevModPhys.14.224
19. [19]
  (19) Ichimura, T.; Mori, Y. Chem. Phys. Lett. 1995, 122, 51. doi: 10.1016/0009-2614(85)85476-2(19) Ichimura, T.; Mori, Y. Chem. Phys. Lett. 1995, 122, 51. doi: 10.1016/0009-2614(85)85476-2
20. [20]
  (20) Ichimura, T.; Mori, Y. J. Chem. Phys. 1997, 107, 835. doi: 10.1063/1.474383(20) Ichimura, T.; Mori, Y. J. Chem. Phys. 1997, 107, 835. doi: 10.1063/1.474383
21. [21]
  (21) Zhu, R. S.; Zhang, H.; Wang, G. J.; Gu, X. B.; Han, K. L.; He, G. Z.; Lou, N. Q. Chem. Phys. 1999, 248, 285.(21) Zhu, R. S.; Zhang, H.; Wang, G. J.; Gu, X. B.; Han, K. L.; He, G. Z.; Lou, N. Q. Chem. Phys. 1999, 248, 285.
22. [22]
  (22) Szaflarski, D. M.; Simon, J. D.; EI-Sayed, M. A. J. Phys. Chem. 1986, 90, 5050. doi: 10.1021/j100412a035(22) Szaflarski, D. M.; Simon, J. D.; EI-Sayed, M. A. J. Phys. Chem. 1986, 90, 5050. doi: 10.1021/j100412a035
23. [23]
  (23) Yang, J. J.; Simon, J. D.; EI-Sayed, M. A. J. Phys. Chem. 1984, 88, 6091. doi: 10.1021/j150669a005(23) Yang, J. J.; Simon, J. D.; EI-Sayed, M. A. J. Phys. Chem. 1984, 88, 6091. doi: 10.1021/j150669a005
24. [24]
  (24) Diau Eric, W. G.; Casanova, J.; Roberts, J. D.; Zewail, A. H. Proc. Natl. Acad. Sci. U. S. A. 2000, 97, 1376. doi: 10.1073/pnas.030524797(24) Diau Eric, W. G.; Casanova, J.; Roberts, J. D.; Zewail, A. H. Proc. Natl. Acad. Sci. U. S. A. 2000, 97, 1376. doi: 10.1073/pnas.030524797
25. [25]
  (25) Kadi, M.; Davidsson, J.; Tarnovsky, A. N.; Rasmusson, M.; Åkesson, E. Chem. Phys. Lett. 2001, 350, 93. doi: 10.1016/S0009-2614(01)01283-0(25) Kadi, M.; Davidsson, J.; Tarnovsky, A. N.; Rasmusson, M.; Åkesson, E. Chem. Phys. Lett. 2001, 350, 93. doi: 10.1016/S0009-2614(01)01283-0
26. [26]
  (26) Yoshida, N.; Hirakawa, Y.; Imasaka, T. Anal. Chem. 2001, 73, 4417. doi: 10.1021/ac010187s(26) Yoshida, N.; Hirakawa, Y.; Imasaka, T. Anal. Chem. 2001, 73, 4417. doi: 10.1021/ac010187s
27. [27]
  (27) Deguchi, T.; Takeyasu, N.; Imasaka, T. Appl. Spectrosc. 2002, 56, 1241. doi: 10.1366/000370202760295511(27) Deguchi, T.; Takeyasu, N.; Imasaka, T. Appl. Spectrosc. 2002, 56, 1241. doi: 10.1366/000370202760295511
28. [28]
  (28) Yuan, L. W.; Zhu, J. Y.; Wang, Y. Q.; Wang, L.; Bai, J. L.; He, G. Z. Chem. Phys. Lett. 2005, 410, 352. doi: 10.1016/j.cplett.2005.05.103(28) Yuan, L. W.; Zhu, J. Y.; Wang, Y. Q.; Wang, L.; Bai, J. L.; He, G. Z. Chem. Phys. Lett. 2005, 410, 352. doi: 10.1016/j.cplett.2005.05.103
29. [29]
  (29) Yuan, L. W.; Wang, Y. Q.; Wang, L.; Bai, J. L.; He, G. Z. Science in China Ser. B: Chemistry 2004, 47, 283. doi: 10.1360/03yb0251(29) Yuan, L. W.; Wang, Y. Q.; Wang, L.; Bai, J. L.; He, G. Z. Science in China Ser. B: Chemistry 2004, 47, 283. doi: 10.1360/03yb0251
30. [30]
  (30) Suzuki, T. J. Phys. B, At. Mol. Opt. Phys. 2014, 47, 124001. doi: 10.1088/0953-4075/47/12/124001(30) Suzuki, T. J. Phys. B, At. Mol. Opt. Phys. 2014, 47, 124001. doi: 10.1088/0953-4075/47/12/124001
31. [31]
  (31) Liu, Z. M.; Hu, C. L.; Li, S.; Xu, Y. Q.; Wang, Y. M.; Zhang, B. Chem. Phys. Lett. 2015, 619, 44. doi: 10.1016/j.cplett. 2014.11.047(31) Liu, Z. M.; Hu, C. L.; Li, S.; Xu, Y. Q.; Wang, Y. M.; Zhang, B. Chem. Phys. Lett. 2015, 619, 44. doi: 10.1016/j.cplett. 2014.11.047
32. [32]
  (32) Shen, H.; Chen, J. J.; Zhang, B. J. Phys. Chem. A 2014, 118, 4444. doi: 10.1021/jp500495b(32) Shen, H.; Chen, J. J.; Zhang, B. J. Phys. Chem. A 2014, 118, 4444. doi: 10.1021/jp500495b
33. [33]
  (33) Qiu, X. J.; Ding, Z. H.; Xu, Y. Q.; Wang, Y. M.; Zhang, B. Phys. Rev. A 2014, 89, 033045.(33) Qiu, X. J.; Ding, Z. H.; Xu, Y. Q.; Wang, Y. M.; Zhang, B. Phys. Rev. A 2014, 89, 033045.
34. [34]
  (34) Abulimiti, B.; Zhu, R. S.; Qiu, X. J.; Qin, C.; Zhang, B. Acta Phys. -Chim. Sin. 2014, 30, 22. [布玛利亚?阿布力米提, 朱荣淑, 邱学军, 秦晨, 张冰. 物理化学学报, 2014, 30, 22.](34) Abulimiti, B.; Zhu, R. S.; Qiu, X. J.; Qin, C.; Zhang, B. Acta Phys. -Chim. Sin. 2014, 30, 22. [布玛利亚?阿布力米提, 朱荣淑, 邱学军, 秦晨, 张冰. 物理化学学报, 2014, 30, 22.]
35. [35]
  (35) Liu, Y. Z.; Knopp, G.; Qin, C. C.; Gerber, T. Chem. Phys. 2015, 446, 142. doi: 10.1016/j.chemphys.2014.11.016(35) Liu, Y. Z.; Knopp, G.; Qin, C. C.; Gerber, T. Chem. Phys. 2015, 446, 142. doi: 10.1016/j.chemphys.2014.11.016
36. [36]
  (36) Liu, B. K.; Wang, Y. Q.; Wang, L. J. Phys. Chem. A 2012, 116, 111. doi: 10.1021/jp209211s(36) Liu, B. K.; Wang, Y. Q.; Wang, L. J. Phys. Chem. A 2012, 116, 111. doi: 10.1021/jp209211s
37. [37]
  (37) Parker, D. H.; Eppink, A. T. J. B. J. Chem. Phys. 1997, 107, 2357. doi: 10.1063/1.474624(37) Parker, D. H.; Eppink, A. T. J. B. J. Chem. Phys. 1997, 107, 2357. doi: 10.1063/1.474624
38. [38]
  (38) Eppink, A. T. J. B.; Parker, D. H. Rev. Sci. Instrum. 1997, 68, 3477. doi: 10.1063/1.1148310(38) Eppink, A. T. J. B.; Parker, D. H. Rev. Sci. Instrum. 1997, 68, 3477. doi: 10.1063/1.1148310
39. [39]
  (39) Qin, C. C.; Liu, Y. Z.; Zhang, S.; Wang, Y. M.; Tang, Y.; Zhang, B. Phys. Rev. A 2011, 83, 033423. doi: 10.1103/PhysRevA. 83.033423(39) Qin, C. C.; Liu, Y. Z.; Zhang, S.; Wang, Y. M.; Tang, Y.; Zhang, B. Phys. Rev. A 2011, 83, 033423. doi: 10.1103/PhysRevA. 83.033423
40. [40]
  (40) Garcia, G. A.; Nahon, L.; Powis, I. Rev. Sci. Instrum. 2004, 75, 4989. doi: 10.1063/1.1807578(40) Garcia, G. A.; Nahon, L.; Powis, I. Rev. Sci. Instrum. 2004, 75, 4989. doi: 10.1063/1.1807578
41. [41]
  (41) O'Keeffe, P.; Bolognesi, P.; Coreno, M.; Moise, A.; Richter, R.; Cautero, G.; Stebel, L.; Ser , R.; Pravica, L.; Ovcharenko, Y.; Avaldi, L. Rev. Sci. Instrum. 2011, 82, 033109. doi: 10.1063/1.3563723(41) O'Keeffe, P.; Bolognesi, P.; Coreno, M.; Moise, A.; Richter, R.; Cautero, G.; Stebel, L.; Ser , R.; Pravica, L.; Ovcharenko, Y.; Avaldi, L. Rev. Sci. Instrum. 2011, 82, 033109. doi: 10.1063/1.3563723
42. [42]
  (42) Zakrzewski, V. G.; Ortiz, J. V. J. Phys. Chem. 1996, 100, 13979. doi: 10.1021/jp960978b(42) Zakrzewski, V. G.; Ortiz, J. V. J. Phys. Chem. 1996, 100, 13979. doi: 10.1021/jp960978b
43. [43]
  (43) Holland, D. M. P.; Powis, I.; Trofimov, A. B.; Bodzuk, I. L.; Soshnikov, D. Y.; Potts, A. W.; Karlsson, L. Chem. Phys. 2015, 448, 61. doi: 10.1016/j.chemphys.2014.11.025
  (43) Holland, D. M. P.; Powis, I.; Trofimov, A. B.; Bodzuk, I. L.; Soshnikov, D. Y.; Potts, A. W.; Karlsson, L. Chem. Phys. 2015, 448, 61. doi: 10.1016/j.chemphys.2014.11.025

扫一扫看文章

计量

PDF下载量: 257
文章访问数: 847
HTML全文浏览量: 36

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

邻二氯苯激发态动力学

English

Dynamics of Excited o-Dichlorobenzene

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

邻二氯苯激发态动力学

English

Dynamics of Excited o-Dichlorobenzene

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs