Salt effect on molecular orientation at air/liquid methanol interface

Xia Li Gang-Hua Deng Rong-Juan Feng Ke Lin Zhen Zhang Yu Bai Zhou Lu Yuan Guo

引用本文: Xia Li,  Gang-Hua Deng,  Rong-Juan Feng,  Ke Lin,  Zhen Zhang,  Yu Bai,  Zhou Lu,  Yuan Guo. Salt effect on molecular orientation at air/liquid methanol interface[J]. Chinese Chemical Letters, 2016, 27(4): 535-539. shu
Citation:  Xia Li,  Gang-Hua Deng,  Rong-Juan Feng,  Ke Lin,  Zhen Zhang,  Yu Bai,  Zhou Lu,  Yuan Guo. Salt effect on molecular orientation at air/liquid methanol interface[J]. Chinese Chemical Letters, 2016, 27(4): 535-539. shu

Salt effect on molecular orientation at air/liquid methanol interface

  • 基金项目:

    This work was financially supported by the National Natural Science Foundation of China (Nos. 21227802, 21303216 and 21473217).

摘要: The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy (SFG-VS). We clarified that the average tilting angle of the methyl group to be θ=30°±5° at the air/pure methanol surface assuming a δ-function orientational distribution. Upon the addition of 3 mol/L NaI, the methyl group tilts further away from the surface normal with a new θ=41°±3°. This orientational change does not explain the enhancement of the SFG-VS intensities when adding NaI, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the NaI concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data.

English

    1. [1] E.M. Knipping, M.J. Lakin, K.L. Foster, et al., Experiments and simulations of ionenhanced interfacial chemistry on aqueous NaCl aerosols, Science 288(2000) 301-306.

    2. [2] B.C. Garrett, Ions at the air/water interface, Science 303(2004) 1146-1147.

    3. [3] P. Jungwirth, B. Winter, Ions at aqueous interfaces:from water surface to hydrated proteins, Ann. Rev. Phys. Chem. 59(2008) 343-366.

    4. [4] T.M. Chang, L.X. Dang, Recent advances in molecular simulations of ion solvation at liquid interfaces, Chem. Rev. 106(2006) 1305-1322.

    5. [5] S. Gopalakrishnan, D.F. Liu, H.C. Allen, M. Kuo, M.J. Shultz, Vibrational spectroscopic studies of aqueous interfaces:salts, acids, bases, and nanodrops, Chem. Rev. 106(2006) 1155-1175.

    6. [6] P. Jungwirth, D.J. Tobias, Specific ion effects at the air/water interface, Chem. Rev. 106(2006) 1259-1281.

    7. [7] L.X. Dang, Ions at the liquid/vapor interface of methanol, J. Phys. Chem. A 108(2004) 9014-9017.

    8. [8] O. Hö fft, A. Borodin, U. Kahnert, et al., Surface segregation of dissolved salt ions, J. Phys. Chem. B 110(2006) 11971-11976.

    9. [9] G. Andersson, H. Morgner, L. Cwiklik, P. Jungwirth, Anions of alkali halide salts at surfaces of formamide solutions:concentration depth profiles and surface topography, J. Phys. Chem. C 111(2007) 4379-4387.

    10. [10] L. Cwiklik, G. Andersson, L.X. Dang, P. Jungwirth, Segregation of inorganic ions at surfaces of polar nonaqueous liquids, ChemPhysChem 8(2007) 1457-1463.

    11. [11] X.Q. Sun, C.D. Wick, L.X. Dang, Computational study of ion distributions at the air/liquid methanol interface, J. Phys. Chem. A 115(2011) 5767-5773.

    12. [12] Z.S. Huang, W. Hua, D. Verreault, H.C. Allen, Salty glycerol versus salty water surface organization:bromide and iodide surface propensities, J. Phys. Chem. A 117(2013) 6346-6353.

    13. [13] X. Zhuang, P.B. Miranda, D. Kim, Y.R. Shen, Mapping molecular orientation and conformation at interfaces by surface nonlinear optics, Phys. Rev. B:Condens. Matter 59(1999) 12632-12640.

    14. [14] Y. Rao, S.Y. Hong, N.J. Turro, K.B. Eisenthal, Molecular orientational distribution at interfaces using second harmonic generation, J. Phys. Chem. C 115(2011) 11678-11683.

    15. [15] Y.R. Shen, Surface spectroscopy by nonlinear optics, in:T.W. Hansch, M. Inguscio (Eds.), Frontiers in Laser Spectroscopy, Elsevier Science Publ. B. V., Amsterdam, 1994, pp. 139-165.

    16. [16] K. Wolfrum, H. Graener, A. Laubereau, Sum-frequency vibrational spectroscopy at the liquid-air interface of methnaol. Water solutions, Chem. Phys. Lett. 213(1993) 41-46.

    17. [17] C.D. Stanners, Q. Du, R.P. Chin, et al., Polar ordering at the liquid-vapor interface of n-alcohols (C1-C8), Chem. Phys. Lett. 232(1995) 407-413.

    18. [18] R. Lü, W. Gan, H.F. Wang, Novel method for accurate determination of the orientational angle of interfacial chemical groups, Chin. Sci. Bull. 48(2003) 2183-2187.

    19. [19] R. Lü, W. Gan, H.F. Wang, Letter to CSB, Chin. Sci. Bull. 49(2004) 899.

    20. [20] H. Chen, W. Gan, R. Lu, Y. Guo, H.F. Wang, Determination of structure and energetics for gibbs surface adsorption layers of binary liquid mixture 2. Methanol+water, J. Phys. Chem. B 109(2005) 8064-8075.

    21. [21] W. Gan, B.H. Wu, H. Chen, Y. Guo, H.F. Wang, Accuracy and sensitivity of determining molecular orientation at interfaces using sum frequency generation vibrational spectroscopy, Chem. Phys. Lett. 406(2005) 467-473.

    22. [22] H.F. Wang, W. Gan, R. Lu, Y. Rao, B.H. Wu, Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS), Int. Rev. Phys. Chem. 24(2005) 191-256.

    23. [23] R.R. Feng, Y. Guo, H.F. Wang, Reorientation of the "free OH" group in the topmost layer of air/water interface of sodium fluoride aqueous solution probed with sum-frequency generation vibrational spectroscopy, J. Chem. Phys. 141(2014) 18C507.

    24. [24] G. Ma, H.C. Allen, Surface studies of aqueous methanol solutions by vibrational broad bandwidth sum frequency generation spectroscopy, J. Phys. Chem. B 107(2003) 6343-6349.

    25. [25] R. Superfine, J.Y. Huang, Y.R. Shen, Nonlinear optical studies of the pure liquid/vapor interface:vibrational spectra and polar ordering, Phys. Rev. Lett. 66(1991) 1066-1069.

    26. [26] M. Matsumoto, Y. Kataoka, Molecular orientation near liquid-vapor interface of methanol:simulational study, J. Chem. Phys. 90(1989) 2398-2407.

    27. [27] X. Li, R.J. Feng, J.J. Wang, et al., Role of refractive index in sum frequency generation intensity of salt solution interfaces, Chin. Chem. Lett. 26(2015) 1542-1546.

  • 加载中
计量
  • PDF下载量:  1
  • 文章访问数:  807
  • HTML全文浏览量:  20
文章相关
  • 发布日期:  2016-01-08
  • 收稿日期:  2015-12-14
  • 修回日期:  2015-12-23
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

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章