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化学进展 2011, Vol. 23 Issue (10): 2151-2159 前一篇   后一篇

• 综述与评论 •

微波波谱法研究分子系统内基团大幅度运动动力学

唐守渊1,2, 付钰洁3, 夏之宁2,4, 李百战1,2*   

  1. 1. 重庆大学三峡库区生态环境教育部重点实验室 重庆 400030;
    2. 重庆大学城市建设与环境工程学院 重庆 400030;
    3. 重庆理工大学药学与生物工程学院 重庆 400050;
    4. 重庆大学化学化工学院 重庆 400044
  • 收稿日期:2011-01-01 修回日期:2011-04-01 出版日期:2011-10-24 发布日期:2011-09-15
  • 作者简介:e-mail:Baizhanli@cqu.edu.cn
  • 基金资助:

    重庆市自然科学基金支持项目(CSTC,2009BB5054)和三峡库区生态环境教育部重点实验室访问学者项目资助

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Exploring Dynamics of Large Amplitude Internal Motions of Molecular Systems by Microwave Spectroscopy

Tang Shouyuan1,2, Fu Yujie3, Xia Zhining2,4, Li Baizhan1,2*   

  1. 1. Key Laboratory of the Three Gorges Reservoir Region's Eco-Environment of Ministry of Education, Chongqing University, Chongqing 400030, China;
    2. College of Urban Construction and Environmental Engineering, Chongqing University, Chongqing 400030, China;
    3. College of Pharmacy and Bioengineering, Chongqing University of Technology, Chongqing 400050, China;
    4. College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China
  • Received:2011-01-01 Revised:2011-04-01 Online:2011-10-24 Published:2011-09-15

分子中基团的运动方式、机制对分子体系性质、分子功能的表达等具有重要作用。微波波谱法在研究分子系统内部动力学、分子结构、构象变化、弱相互作用、基团大幅度运动以及探索量子溶剂等方面具有独特的能力,特别适合研究分子的精细结构、分子系统基团的内部转动运动,具有高灵敏度、高分辨率的特点。本文讨论了微波波谱法在研究分子系统基团大幅度运动动力学方面的应用,包括分子系统中甲基基团的内部转动、OH基团的运动、氨和氨基化合物的反演以及环状有机分子环运动等的动力学,同时结合作者使用微波波谱法研究的部分体系进行了分析。

关键词： 微波波谱, 分子系统, 大幅度运动, 相互作用, 内部动力学

Molecular group internal rotation and dynamics are of great significance in the expression of the activity and function of the molecules. Microwave spectroscopy which is capable of investigating the internal dynamics of molecular systems, the systematic structure of molecules, the conformation equilibria, weakly bound interactions, large amplitude motions, and quantum solvation mechanism, is a kind of technique with high sensitivity and resolution for studying group internal rotation dynamics and hyperfine structure of molecules. The large amplitude internal motions of molecular systems can be observed in their rotational spectra are reviewed in this paper. The typical motions are internal motion of methyl groups, internal motion of OH groups, inversion of amines and amides, organic ring motions and pseudorotation. Some our investigations are also discussed.

Contents
1 Introduction
2 Internal large amplitude motion of symmetric group
2.1 Internal large amplitude motion of single methyl group
2.2 Internal large amplitude motion of two and three methyl groups
2.3 Interplay of internal motion of methyl group with other motions
3 Internal motion of hydroxyl group
3.1 Internal large amplitude motion of hydroxyl group in organic ring
3.2 Internal motion of hydroxyl group in spherical top molecules
3.3 Internal motion of hydroxyl group in transient chiral molecules
4 Inversion of amines and other internal motions
5 Organic ring motions
5.1 Four- and five-membered ring puckering
5.2 Pseudorotation of organic ring
6 Conclusion and outlook

Key words: microwave spectroscopy, molecular systems, large amplitude motions, interaction, internal dynamics

中图分类号: 

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[1] 唐守渊(Tang S Y), 夏之宁(Xia Z N), 付钰洁(Fu Y J), 勾茜(Gou Q). 化学进展(Progress in Chemistry), 2009,21(5):1060-1069
[2] Dian B C, Brown G G, Douglass K O, Pate B H. Science, 2008, 320(5878): 924-928
[3] Schnell M, Grabow J U. Angew. Chem. Int. Ed., 2006, 45(21): 3465-3470
[4] Suma K, Sumiyoshi Y, Endo Y. Science, 2006, 311(5765): 1278-1281
[5] Baughcum S L, Smith Z, Wilson E B, Duerst R W. J. Am. Chem. Soc., 1984, 106(8): 2260-2264
[6] Suma K, Sumiyoshi Y, Endo Y. Science, 2005, 308(24): 1885-1886
[7] Melandri S, Evangelisti L, Maris A, Caminati W, Giuliano B M, Feyer V, Prince K C, Coreno M. J. Am. Chem. Soc., 2010, 132 (30):10269-10271
[8] Sanchez R, Giuliano B M, Melandri S, Favero L B, Caminati W. J. Am. Chem. Soc., 2007, 129(19): 6287-6290
[9] Maris A, Giuliano B M, Bonazzi D, Caminati W. J. Am. Chem. Soc., 2008, 130 (42): 13860-13861
[10] Tang S Y, Evangelisti L, Velino B, Caminati W. J. Chem. Phys., 2008, 129(14), 144301-144306
[11] Blanco S, Melandri S, Ottaviani P, Caminati W. J. Am. Chem. Soc., 2007, 129(9):2700-2703
[12] Tang J, Xu Y, Mckellar W A R, Jäger W. Science, 2002, 297(5589): 2030-2033
[13] Schwartz P R, Bevilacqua R M, Croskey C L, Olivero J J. Nature, 1983, 305(22): 294-295
[14] Cleeton C E, Williams N H. Phys. Rev., 1934, 45(2): 234-237
[15] Gordy W, Cook R L. Microwave molecular spectra. 2nd ed., New York: Wiley Interscience, 1984, 11-209
[16] Caminati W, Cazzoli G, Mirri A M. Chem. Phys. Letters, 1975, 31(1): 104-107
[17] Caminati W, Scappini F. J. Mol. Spectrosc., 1986, 117(2): 184-194
[18] Xu L H, Lees R M, Hougen J T. J. Chem. Phys., 1999, 110(8): 3835-3841
[19] Kleiner I, Hougen J T, Grabow J U, Belov S P, Tretyakov M, Cosléou J. J. Mol. Spectrosc., 1996, 179(1): 41-60
[20] Xu L H, Hougen J T. J. Mol. Spectrosc., 1995, 173(2): 540-551
[21] Hellweg A. Chem. Phys., 2008, 344(3):281-290
[22] Hellweg A, Hättig C. J. Chem. Phys., 2007, 127(2): 024307-024316
[23] Kawashima Y, Suenram R D, Hirota E. J. Mol. Spectrosc., 2003, 219(1):105-118
[24] Ohashi N, Hougen J T, Suenram R D, Lovas F J, Kawashima Y, Fujitake M, Pyka J. J. Mol. Spectrosc., 2004, 227(1): 28-42
[25] Fujitake M, Kubota Y, Ohashi N. J. Mol. Spectrosc., 2006, 236(1): 97-109
[26] Groner P, Herbst E, de Lucia F C, Drouin B J, Mäder H. J. Mol. Struct., 2006, 795(1/3): 173-178
[27] Schnell M, Grabow J U. Phys. Chem. Chem. Phys., 2006, 8: 2225-2231
[28] Schnell M, Grabow J U. Chem. Phys., 2008, 343(2/3): 121-128
[29] Caminati W, Grabow J U. J. Am. Chem. Soc., 2006, 128(3):854-857
[30] Evangelisti L, Tang S Y, Velino B, Giuliano B M, Melandri S, Caminati W. Chem. Phys. Letters, 2009, 473(4/6): 247-250
[31] Caminati W. J. Mol. Spectrosc., 1981, 90(2): 315-320
[32] Fantoni A C, Caminati W, Meyer R. Chem. Phys. Letters, 1987, 133(1): 27-33
[33] Caminati W, Meyer R. J. Mol. Spectrosc., 1981, 90(2): 303-314
[34] Mathier E, Bauder A, Günthard H H. J. Mol. Spetrosc., 1971, 37(1): 63-76
[35] Sanchez R, Giuliano B M, Melandri S, Caminati W. Chem. Phys. Letters, 2006, 425(1/3): 6-9
[36] Lesarri A, Shipman S T, Neill J L, Brown G G, Suenram R D, Kang L, Caminati W, Pate B H. J. Am. Chem. Soc., 2010, 132(38):13417-13424
[37] Tang S Y, Xia Z N, Maris A, Caminati W. Chem. Phys. Letters, 2010, 498(1/3): 52-55
[38] Evangelisti L, Favero L B, Caminati W. J. Mol. Struct., 2010, 978(1/3): 279-281
[39] Utzat K A, Bohn R K, Montgomery J A, Michels H H, Caminati W. J. Phys. Chem. A, 2010, 114(25): 6913-6916
[40] Oh J J, Drouin B J, Cohen E A. J. Mol. Spetrosc., 2005, 234(1): 10-24
[41] Cohen E A, Drouin B J, Valenzuela E A, Woods R C, Caminati W, Maris A, Melandri S. J. Mol. Spectrosc., 2010, 260(1): 77-83
[42] Tang S Y, Camianti W. Phys. Chem. Chem. Phys.,2011,13(20): 9137-9139
[43] Quack M. Angew. Chem. Int. Ed., 2005, 44(23): 3623-3626
[44] Snow M S, Howard B J, Evangelisti L, Caminati W. J. Phys. Chem. A, 2011, 115(1): 47-51
[45] Pearson J C, Sastry K V L N, Herbst E, De Lucia F C. J. Mol. Spetrosc., 1996, 175(2): 246-261
[46] Melandri S, Favero P G, Caminati W. Chem. Phys. Letters, 1994, 223(5/6): 541-545
[47] Hirota E, Kawashima Y. J. Mol. Spetrosc., 2001, 207(2): 243-253
[48] Wollrab J E, Laurie V W. J. Chem. Phys., 1968, 48(11):5058-5067
[49] Grabow J U, Andrews A M, Fraser G T, Irikura K K, Suenram R D, Lovas F J, Lafferty W J, Domenech J L. J. Chem. Phys., 1996, 105(17): 7249-7262
[50] Tang S Y, Evangelisti L, Caminati W. J. Mol. Spectrosc., 2009, 258(1/2): 71-74
[51] Chan S I, Zinn J, Fernandez J, Gwinn W D. J. Chem. Phys., 1960, 33(6): 1643-1655
[52] Harris D O, Harrington H W, Luntz A C, Gwinn W D. J. Chem. Phys., 1966, 44(9): 3467-3480
[53] Vogelsanger B, Caminati W, Bauder A. Chem. Phys. Letters, 1987, 141(3): 245-250
[54] Caminati W, Vogelsanger B, Meyer R, Grassi G, Bauder A. J. Mol. Spectrosc., 1988, 131(1): 172-184
[55] López J C, Alonso J L, Charro M E, Wlodarczak G, Demaison J. J. Mol. Spetrosc., 1992, 155(1): 143-157
[56] Hassan K H, Hollas J M. J. Mol. Spetrosc., 1991, 147(1):100-113
[57] Caminati W, Damiani D, Corbelli G, Favero L B. Mol. Physics, 1992, 75: 857-865
[58] Caminati W, Favero L B, Velino B, Zerbetto F. Mol. Physics, 1993, 78: 1561-1574
[59] Caminati W, Damiani D, Favero L B. Mol. Physics, 1993, 76: 699-708
[60] Caminati W, Melandri S, Corbelli G, Favero L B, Meyer R. Mol. Physics, 1993, 80: 1297-1315
[61] Ottaviani P, Caminati W. Chem. Phys. Letters, 2005, 405(1/3): 68-72
[62] Kilpatrick J E, Pitzer K S, Spitzer R. J. Am. Chem. Soc., 1947, 69(10):2483-2488
[63] Harris D O, Engerholm G, Tolman C, Luntz A, Keller R, Kim H, Gwinn W D. J. Chem. Phys., 1969, 50(6):2438-2446
[64] Dommen J, Brupbacher J, Grassi G, Bauder A. J. Am. Chem. Soc., 1990, 112(3): 953-957
[65] Meyer R, López J C, Alonso J L, Melandri S, Favero P G, Caminati W. J. Chem. Phys., 1999, 111(17): 7871-7880
[66] Melnik D G, Gopalakrishnan S, Miller T A, de Lucia F C. J. Chem. Phys., 2003, 118(8): 3589-3599
[67] Melnik D G, Miller T A, de Lucia F C. J. Mol. Spetrosc., 2003, 221(2): 227-238
[68] Melnik D G, Miller T A. Science, 2008, 320(5878): 881-882
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