N2O+离子B2П态的光谱与光解离动力学

doi:10.3866/PKU.WHXB201503041

物理化学学报 >> 2015, Vol. 31 >> Issue (5): 829-835.doi: 10.3866/PKU.WHXB201503041

N₂O⁺离子B²П态的光谱与光解离动力学

孙中发, 高治, 吴向坤, 唐国强, 周晓国, 刘世林

中国科学技术大学化学物理系, 合肥微尺度物质科学国家实验室(筹), 合肥230026

收稿日期:2015-01-05 修回日期:2015-03-03 发布日期:2015-05-08
通讯作者: 周晓国 E-mail:xzhou@ustc.edu.cn
基金资助:
国家自然科学基金(21373194)和国家重点基础研究发展规划项目(973) (2013CB834602)资助

Excitation Spectra and Photodissociation Dynamics of the B²П State of the N₂O⁺ Ion

SUN Zhong-Fa, GAO Zhi, WU Xiang-Kun, TANG Guo-Qiang, ZHOU Xiao-Guo, LIU Shi-Lin

Hefei National Laboratory for Physical Sciences at Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China

Received:2015-01-05 Revised:2015-03-03 Published:2015-05-08
Contact: ZHOU Xiao-Guo E-mail:xzhou@ustc.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (21373194) and National Key Basic Research Program of China (973) (2013CB834602).

摘要/Abstract

摘要：

用一束波长为360.55 nm的激光直接作用于超声射流的N₂O分子束, 通过(3+1)共振增强多光子电离(REMPI)过程制备纯净的N₂O⁺(X²П(0,0,0))母体离子, 再用另一束波长在243-278 nm范围的激光将母体离子激发至B²П态后解离. 扫描解离激光波长, 监测NO⁺离子碎片的强度, 从而获得N₂O⁺离子B²П态的光致碎片激发(PHOFEX)谱. 通过拟合转动分辨光谱, 得到了相应的转动常数和自旋分裂常数, 从而区分了A²Σ⁺态高振动能级和B²П态带源的贡献, 明确了N₂O⁺离子B²П态的光谱"带头"位置(37154 cm^-1), 并将获得的振动光谱初步归属为B²П(v₁,v₂,v₃)←X²П的振动跃迁序列. 通过对NO⁺碎片离子的飞行时间质谱峰形的分析, 还获得了解离过程中释放的平均平动能, 并结合电子激发态势能面, 讨论了N₂O⁺离子B²П态的解离机理.

关键词: N₂O⁺离子, 共振增强多光子电离, 振动光谱, 飞行时间质谱, 光解离

Abstract:

N₂O⁺ ions in the X²П(0,0,0) ground state were prepared by (3+1) resonance-enhanced multiphoton ionization (REMPI) of jet-cooled N₂O molecules at 360.55 nm, and then photoexcited to various vibrational levels in the B²П state over a wavelength range of 243-278 nm, followed by dissociation. The photofragment excitation (PHOFEX) spectrum was recorded by measuring the intensity of NO⁺ ion fragments vs excitation wavelength. The rotational constants and spin-orbit coupling were obtained by fitting the rotational structures of the vibrational bands. Thus, the contributions of highly excited vibronic levels of A²Σ⁺ states were distinguished from the other bands, and the original band of B²П state was verified. The series of vibrational bands in the PHOFEX spectrum were assigned to the transition of B²П(v₁,v₂,v₃) ←X²П. The average released kinetic energy of dissociation from the various B²П(v₁,v₂,v₃) ionic states was obtained by fitting the spreading contour of the NO⁺ ion peak in time-of-flight mass spectra. Dissociation mechanisms of N₂O⁺(B²П) were proposed with the aid of the theoretical potential energy surfaces of N₂O⁺ ions.

Key words: N₂O⁺ ion, Resonance enhanced multiphoton ionization, Vibrational spectroscopy, Time-of-flight mass spectrum, Photodissociation

孙中发, 高治, 吴向坤, 唐国强, 周晓国, 刘世林. N₂O⁺离子B²П态的光谱与光解离动力学[J]. 物理化学学报, 2015, 31(5), 829-835. doi: 10.3866/PKU.WHXB201503041

SUN Zhong-Fa, GAO Zhi, WU Xiang-Kun, TANG Guo-Qiang, ZHOU Xiao-Guo, LIU Shi-Lin. Excitation Spectra and Photodissociation Dynamics of the B²П State of the N₂O⁺ Ion[J]. Acta Phys. -Chim. Sin. 2015, 31(5), 829-835. doi: 10.3866/PKU.WHXB201503041

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201503041

https://www.whxb.pku.edu.cn/CN/Y2015/V31/I5/829

参考文献

(1) Burley, J. D.; Ervin, K. M.; Armentrout, P. B. J. Chem. Phys. 1987, 86, 1944. doi: 10.1063/1.452144
(2) Hopper, D. G. J. Am. Chem. Soc. 1978, 100, 1019. doi: 10.1021/ja00472a001
(3) Komiha, N. J. Mol. Struc. -Theochem1994, 112, 313.
(4) Li, X.; Huang, Y. L.; Flesch, G. D.; Ng, C. Y. J. Chem. Phys. 1997, 106, 1373. doi: 10.1063/1.474087
(5) Danis, P. O.; Wyttenbach, T.; Maier, J. P. J. Chem. Phys. 1988, 88, 3451. doi: 10.1063/1.453893
(6) Patsilinakou, E.; Wiedmann, R. T.; Fotakis, C.; Grant, E. R. J. Chem. Phys. 1989, 91, 3916. doi: 10.1063/1.456823
(7) Scheper, C. R.; Kuijt, J.; Buma, W. J.; de Lange, C. A. J. Chem. Phys. 1998, 109, 7844. doi: 10.1063/1.477431
(8) Szarka, M. G.; Wallace, S. C. J. Chem. Phys. 1991, 95, 2336. doi: 10.1063/1.460940
(9) Dehmer, P. M.; Dehmer, J. L.; Chupka, W. A. J. Chem. Phys. 1980, 73, 126. doi: 10.1063/1.439906
(10) Locht, R.; Caprace, G.; Momigny, J. Chem. Phys. Lett.1984, 111, 560. doi: 10.1016/0009-2614(84)80271-7
(11) Turner, D.W.; May, D. P. J. Chem. Phys. 1967, 46, 1156. doi: 10.1063/1.1840783
(12) Weiss, M. J. Chem. Phys. Lett. 1976, 39, 250. doi: 10.1016/0009-2614(76)80066-8
(13) Chen, W.W.; Liu, J. B.; Ng, C. Y. J. Phys. Chem. A 2003, 107, 8086. doi: 10.1021/jp022389d
(14) Wiedmann, R. T.; Grant, E. R.; Tonkyn, R. G.; White, M. G. J. Chem. Phys. 1991, 95, 746. doi: 10.1063/1.461080
(15) Kong, W.; Rodgers, D.; Hepburn, J.W. Chem. Phys. Lett. 1994, 221, 301. doi: 10.1016/0009-2614(94)00260-6
(16) Kinmond, E.; Eland, J. H. D.; Karlsson, L. Int. J. Mass Spectrom. 1999, 185, 437.
(17) Tang, X. F.; Niu, M. L.; Zhou, X. G.; Liu, S. L.; Liu, F. Y.; Shan, X. B.; Sheng, L. S. J. Chem. Phys. 2011, 134, 054312. doi: 10.1063/1.3549130
(18) Richardviard, M.; Delboulbe, A.; Vervloet, M. Chem. Phys. 1996, 209, 159. doi: 10.1016/0301-0104(96)00164-4
(19) Nenner, I.; Guyon, P. M.; Baer, T.; Govers, T. R. J. Chem. Phys. 1980, 72, 6587. doi: 10.1063/1.439115
(20) Chiang, S. Y.; Ma, C. I. J. Phys. Chem. A 2000, 104, 1991. doi: 10.1021/jp9935081
(21) Richardviard, M.; Atabek, O.; Dutuit, O.; Guyon, P. M. J. Chem. Phys. 1990, 93, 8881. doi: 10.1063/1.459227
(22) Xu, H. F.; Li, Q. F.; Zhou, X. G.; Dai, J. H.; Liu, S. L.; Ma, X. X. Acta Phys. Sin. 2004, 53, 1759. [徐海峰, 李奇峰, 周晓国, 戴静华, 刘世林, 马兴孝. 物理学报, 2004, 53, 1759.]
(23) Xu, H. F.; Guo, Y.; Li, Q. F.; Shi, Y.; Liu, S. L.; Ma, X. X. J. Chem. Phys. 2004, 121, 3069. doi: 10.1063/1.1772363
(24) Xu, H. F.; Guo, Y.; Li, Q. F.; Liu, S. L.; Ma, X. X.; Liang, J.; Li, H. Y. J. Chem. Phys. 2003, 119, 11609. doi: 10.1063/1.1624596
(25) Wang, H.; Zhou, X. G.; Liu, S. L.; Jiang, B.; Dai, D. X.; Yang, X. M. J. Chem. Phys. 2010, 132, 244309. doi: 10.1063/1.3457945
(26) Wang, H.; Liu, S. L.; Liu, J.; Wang, F. Y.; Jiang, B.; Yang, X. M. Acta Phys. Sin. 2008, 57, 796. [汪华, 刘世林, 刘杰, 王凤燕, 姜波, 杨学明. 物理学报, 2008, 57, 796.]
(27) Xu, H. F.; Guo, Y.; Li, Q. F.; Dai, J. H.; Liu, S. L.; Ma, X. X.; Liang, J.; Li, H. Y. Acta Phys. Sin. 2004, 53, 1027. [徐海峰, 郭颖, 李奇峰, 戴静华, 刘世林, 马兴孝, 梁军, 李海洋. 物理学报, 2004, 53, 1027.]
(28) Brundle, C.; Turner, D. Int. J. Mass Spectrom. Ion Phys. 1969, 2, 195. doi: 10.1016/0020-7381(69)80018-5
(29) Lorquet, A. J.; Lorquet, J. C.; Wankenne, H.; Momigny, J.; Lefebvre, H. J. Chem. Phys. 1971, 55, 4053. doi: 10.1063/1.1676699
(30) Koppel, H.; Cederbaum, L. S.; Domcke, W. Chem. Phys. 1982, 69, 175. doi: 10.1016/0301-0104(82)88144-5
(31) Cvitas, T.; Klasinc, L.; Kovac, B.; McDiarmid, R. J. Chem. Phys. 1983, 79, 1565. doi: 10.1063/1.446028
(32) Lebech, M.; Houver, J. C.; Dowek, D.; Lucchese, R. R. J. Chem. Phys. 2004, 120, 8226. doi: 10.1063/1.1651087
(33) Tang, X. F.; Zhou, X. G.; Niu, M. L.; Liu, S. L.; Sun, J. D.; Shan, X. B.; Liu, F. Y.; Sheng, L. S. Rev. Sci. Inst. 2009, 80, 113101. doi: 10.1063/1.3250872
(34) Imamura, T.; Imajo, T.; Koyano, I. J. Phys. Chem. 1995, 99, 15465. doi: 10.1021/j100042a020
(35) Lerme, J.; Abed, S.; Holt, R. A.; Larzilliere, M.; Carre, M. Chem. Phys. Lett 1983, 96, 403. doi: 10.1016/0009-2614(83)80717-9
(36) Tokue, I.; Kobayashi, M.; Ito, Y. J. Chem. Phys. 1992, 96, 7458.
(37) Frey, R.; Gotchev, B.; Peatman, W. B.; Pollak, H.; Schlag, E.W. Chem. Phys. Lett. 1978, 54, 411. doi: 10.1016/0009-2614(78)85250-6
(38) Callomon, J. H.; Creutzbe, F. Phil. Trans. R. Soc. A 1974, 277, 157. doi: 10.1098/rsta.1974.0048
(39) Hill, E.; Van Vleck, J. H. Phys. Rev. 1928, 32, 0250. doi: 10.1103/PhysRev.32.250
(40) Mulliken, R. S. Rev. Mod. Phys. 1930, 2, 0060. doi: 10.1103/RevModPhys.2.60
(41) Wang, H. Ion Velocity Imaging Studies on Photodissociation Dynamics of Small Molecules. Ph. D. Dissertation, University of Science and Technology of China, Hefei, 2007. [汪华. 基于离子速度成像技术的小分子光解动力学研究[D]. 合肥: 中国科学技术大学, 2007.]
(42) Aarts, J. F. M.; Callomon, J. H. Mol. Phys. 1987, 62, 637. doi: 10.1080/00268978700102451
(43) Wang, H. F. Ion Velocity Imaging Studies on Photodissociation Dynamics of Small Molecules. Ph. D. Dissertation, University of Science and Technology of China, Hefei, 2007. [徐海峰. CH₂I₂分子和N₂O⁺离子的光解离动力学研究[D]. 合肥: 中国科学技术大学, 2002.]
(44) Chambaud, G.; Gritli, H.; Rosmus, P.; Werner, H. J.; Knowles, P. J. Mol. Phys. 2000, 98, 1793.

[1]	陈文琼, 关永吉, 张姣, 裴俊捷, 张晓萍, 邓友全. 外电场作用下离子液体振动光谱变化的分子动力学模拟研究[J]. 物理化学学报, 2021, 37(10): 2001004 - .
[2]	刘宁亮,沈环. 飞秒脉冲作用下氯丙烯的多光子解离和电离动力学[J]. 物理化学学报, 2017, 33(3): 500 -505 .
[3]	吴向坤,高治,于同坡,周晓国,刘世林. 氧硫化碳在230nm光激发下的S(³P)解离通道[J]. 物理化学学报, 2017, 33(10): 2004 -2012 .
[4]	陈海龙,边红涛,郑俊荣. 基于超快多维振动光谱技术解析分子体系的三维空间构型[J]. 物理化学学报, 2017, 33(1): 40 -62 .
[5]	蔡开聪,郑轩,刘亚男,留珊红,杜芬芬. 甘氨酸二肽分子酰胺-Ⅰ带光谱与结构相关性[J]. 物理化学学报, 2016, 32(5): 1289 -1296 .
[6]	吴沛颖,曾圣渊,蔡青妘,曾文碧. 2, 5-二氟苯酚分子之旋转异构物的质量分辨阈值电离光谱[J]. 物理化学学报, 2016, 32(4): 893 -900 .
[7]	叶传香,马会利,梁万珍. 几个荧光蛋白发色团双光子吸收性质的理论研究[J]. 物理化学学报, 2016, 32(1): 301 -312 .
[8]	吴丹, 张立敏, 周丹娜. N₂O⁺经由B²П_i←X²П跃迁的光解离机理研究[J]. 物理化学学报, 2014, 30(8): 1575 -1580 .
[9]	秦晨, 曾圣渊, 张冰, 曾文碧. 间甲基苯甲醚分子旋转异构体的质量分辨阈值电离光谱[J]. 物理化学学报, 2014, 30(8): 1416 -1425 .
[10]	卢晓林, 周杰, 李柏霖. 不同受限状态下链硫醇的非线性光学响应[J]. 物理化学学报, 2014, 30(12): 2342 -2348 .
[11]	李丹, 薛佳丹, 郑旭明. 4-硝基咪唑A-带激发态结构动力学[J]. 物理化学学报, 2014, 30(12): 2216 -2223 .
[12]	李明娟, 刘明霞, 郑旭明. 1-甲基胸腺嘧啶A-带结构动力学[J]. 物理化学学报, 2013, 29(05): 903 -910 .
[13]	蔡开聪, 留珊红, 刘的文, 林深. 丙氨酸二肽分子二级结构与振动光谱特性[J]. 物理化学学报, 2012, 28(08): 1837 -1842 .
[14]	郭晓楠, 杜蕊, 赵彦英, 裴克梅, 王惠刚, 郑旭明. 2-硫代嘧啶酮和2-硫代吡啶酮在B-吸收带中的动态结构[J]. 物理化学学报, 2012, 28(07): 1570 -1578 .
[15]	周丹娜, 陈琳, 吴丹, 张立敏. OCS⁺经由A²П←X²П激发的光解离光谱[J]. 物理化学学报, 2012, 28(04): 963 -970 .

N₂O⁺离子B²П态的光谱与光解离动力学

Excitation Spectra and Photodissociation Dynamics of the B²П State of the N₂O⁺ Ion

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0