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Journal of Chemical Physics / Volume 136 / Issue 1 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation
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J. Chem. Phys. 136, 014501 (2012); http://dx.doi.org/10.1063/1.3665140 (8 pages)

Influence of solute-solvent coordination on the orientational relaxation of ion assemblies in polar solvents

Minbiao Ji1,2, Robert W. Hartsock1,3, Zheng Sung1, and Kelly J. Gaffney1

1PULSE Institute, SLAC National Accelerator Laboratory, Stanford University, Stanford, California 94305, USA
2Department of Physics, Stanford University, Stanford, California 94305, USA
3Department of Chemistry, Stanford University, Stanford, California 94305, USA

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(Received 5 August 2011; accepted 10 November 2011; published online 3 January 2012)

We have investigated the rotational dynamics of lithium thiocyanate (LiNCS) dissolved in various polar solvents with time and polarization resolved vibrational spectroscopy. LiNCS forms multiple distinct ionic structures in solution that can be distinguished with the CN stretch vibrational frequency of the different ionic assemblies. By varying the solvent and the LiNCS concentration, the number and type of ionic structures present in solution can be controlled. Control of the ionic structure provides control over the volume, shape, and dipole moment of the solute, critical parameters for hydrodynamic and dielectric continuum models of friction. The use of solutes with sizes comparable to or smaller than the solvent molecules also helps amplify the sensitivity of the measurement to the short-ranged solute-solvent interaction. The measured orientational relaxation dynamics show many clear and distinct deviations from simple hydrodynamic behavior. All ionic structures in all solvents exhibit multi-exponential relaxation dynamics that do not scale with the solute volume. For Lewis base solvents such as benzonitrile, dimethyl carbonate, and ethyl acetate, the observed dynamics strongly show the effect of solute-solvent complex formation. For the weak Lewis base solvent nitromethane, we see no evidence for solute-solvent complex formation, but still see strong deviation from the predictions of simple hydrodynamic theory.

© 2012 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. EXPERIMENTAL AND THEORETICAL METHODS
  3. RESULTS
    1. Vibrational spectroscopy
    2. Pump-probe measurements of orientational relaxation
  4. DISCUSSION
  5. CLOSING REMARKS

RELATED DATABASES

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KEYWORDS and PACS

Keywords

dielectric polarisation, dissolving, electric moments, friction, lithium compounds, organic compounds, solvation, solvent effects, time resolved spectra, vibrational modes

PACS

  • 82.30.Nr

    Association, addition, insertion, cluster formation

  • 77.84.Jd

    Polymers; organic compounds

  • 78.47.D-

    Time resolved spectroscopy (>1 psec)

  • 63.20.-e

    Phonons in crystal lattices

  • 77.22.Ej

    Polarization and depolarization

  • 64.75.Bc

    Solubility

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3665140

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

  1. B. Bagchi and R. Biswas, Adv. Chem. Phys. 109, 207 (1999). [ISI] [CAS]
  2. E. A. Carter and J. T. Hynes, J. Chem. Phys. 94, 5961 (1991)JCPSA6000094000009005961000001;, G. R. Fleming and M. H. Cho, Annu. Rev. Phys. Chem. 47, 109 (1996).
  3. M. L. Horng, J. A. Gardecki, A. Papazyan, and M. Maroncelli, J. Phys. Chem. 99, 17311 (1995).
  4. M. Maroncelli, J. Mol. Liq. 57, 1 (1993); [ISI] [CAS]
    J. D. Simon, Acc. Chem. Res. 21, 128 (1988). [ISI] [CAS]
  5. D. Ben-Amotz and J. M. Drake, J. Chem. Phys. 89, 1019 (1988)JCPSA6000089000002001019000001. [ISI] [CAS]
  6. M. L. Horng, J. A. Gardecki, and M. Maroncelli, J. Phys. Chem. A 101, 1030 (1997).
  7. R. S. Hartman and D. H. Waldeck, J. Phys. Chem. 98, 1386 (1994). [ISI] [CAS]
  8. E. W. Castner and M. Maroncelli, J. Mol. Liq. 77, 1 (1998). [Inspec] [ISI] [CAS]
  9. R. Karmakar and A. Samanta, J. Phys. Chem. A 106, 4447 (2002). [ISI] [CAS]
  10. L. R. Narasimhan, K. A. Littau, D. W. Pack, Y. S. Bai, A. Elschner, and M. D. Fayer, Chem. Rev. 90, 439 (1990). [ISI] [CAS]
  11. D. P. Zhong, S. K. Pal, and A. H. Zewail, Chem. Phys. Lett. 503, 1 (2011);, P. Abbyad, W. Childs, X. H. Shi, and S. G. Boxer, Proc. Natl. Acad. Sci. U.S.A. 104, 20189 (2007).
  12. K. B. Eisenthal, Chem. Rev. 96, 1343 (1996); [MEDLINE]
    S. H. Liu, A. D. Miller, K. J. Gaffney, P. Szymanski, S. Garrett-Roe, I. Bezel, and C. B. Harris, J. Phys. Chem. B 106, 12908 (2002); [Inspec] [ISI]
    A. D. Miller, I. Bezel, K. J. Gaffney, S. Garrett-Roe, S. H. Liu, P. Szymanski, and C. B. Harris, Science 297, 1163 (2002). [MEDLINE]
  13. N. E. Levinger and L. A. Swafford, Annu. Rev. Phys. Chem. 60, 385 (2009). [MEDLINE] [CAS]
  14. L. Lehr, M. T. Zanni, C. Frischkorn, R. Weinkauf, and D. M. Neumark, Science 284, 635 (1999). [Inspec] [ISI] [MEDLINE] [CAS]
  15. C. M. Hu and R. Zwanzig, J. Chem. Phys. 60, 4354 (1974)JCPSA6000060000011004354000001. [ISI] [CAS]
  16. D. Kivelson, in Rotational Dynamics of Small and Macromolecules, edited by T. Dorfmuller and R. Pecora (Springer-Verlag, Berlin, 1987), vol. 293, p. 1.
  17. M. G. Kurnikova, N. Balabai, D. H. Waldeck, and R. D. Coalson, J. Am. Chem. Soc. 120, 6121 (1998). [ISI] [CAS]
  18. M. I. Sluch, M. M. Somoza, and M. A. Berg, J. Phys. Chem. B 106, 7385 (2002). [Inspec] [ISI]
  19. J. Dote, D. Kivelson, and R. N. Schwartz, J. Phys. Chem. 85, 2169 (1981). [Inspec] [ISI] [CAS]
  20. A. Gierer and K. Wirtz, Z. Naturforsch. 8, 532 (1953).
  21. J. B. Hubbard and P. G. Wolynes, J. Chem. Phys. 69, 998 (1978)JCPSA6000069000003000998000001.
  22. H. J. Bakker, Chem. Rev. 108, 1456 (2008); [MEDLINE]
    A. W. Omta, M. F. Kropman, S. Woutersen, and H. J. Bakker, Science 301, 347 (2003); [MEDLINE]
    D. E. Moilanen, E. E. Fenn, Y. S. Lin, J. L. Skinner, B. Bagchi, and M. D. Fayer, Proc. Natl. Acad. Sci. U.S.A. 105, 5295 (2008); [MEDLINE]
    H. S. Tan, I. R. Piletic, and M. D. Fayer, J. Chem. Phys. 122, 174501 (2005)JCPSA6000122000017174501000001. [MEDLINE]
  23. M. B. Ji and K. J. Gaffney, J. Chem. Phys. 134, 044516 (2011)JCPSA6000134000004044516000001; [MEDLINE]
    M. B. Ji, M. Odelius, and K. J. Gaffney, Science 328, 1003 (2010);, S. Park, M. Odelius, and K. J. Gaffney, J. Phys. Chem. B 113, 7825 (2009). [Inspec]
  24. K. J. Gaffney, M. B. Ji, M. Odelius, S. Park, and Z. Sun, Chem. Phys. Lett. 504, 1 (2011).
  25. D. Paoli, M. Lucon, and M. Chabanel, Spectrochim. Acta A 34, 1087 (1978).
  26. M. Chabanel and Z. Wang, J. Phys. Chem. 88, 1441 (1984);, M. Chabanel, M. Lucon, and D. Paoli, J. Phys. Chem. 85, 1058 (1981).
  27. J. Barthel, R. Buchner, and E. Wismeth, J. Solution Chem. 29, 937 (2000).
  28. M. B. Ji, S. Park, and K. J. Gaffney, J. Phys. Chem. Lett. 1, 1771 (2010).
  29. S. Park, M. B. Ji, and K. J. Gaffney, J. Phys. Chem. B 114, 6693 (2010).
  30. K. Ohta and K. Tominaga, Chem. Phys. Lett. 429, 136 (2006);, M. Li, J. Owrutsky, M. Sarisky, J. P. Culver, A. Yodh, and R. M. Hochstrasser, J. Chem. Phys. 98, 5499 (1993);, V. Lenchenkov, C. X. She, and T. Q. Lian, J. Phys. Chem. B 110, 19990 (2006); [Inspec]
    K. Dahl, G. M. Sando, D. M. Fox, T. E. Sutto, and J. C. Owrutsky, J. Chem. Phys. 123 (2005)JCPSA6000123000008084504000001. [ISI] [MEDLINE]
  31. M. B. Ji, R. W. Hartsock, Z. Sun, and K. J. Gaffney, J. Phys. Chem. B 115, 11399 (2011).
  32. C. F. Guerra, J. G. Snijders, G. te Velde, and E. J. Baerends, Theor. Chem. Acc. 99, 391 (1998);, G. T. Velde, F. M. Bickelhaupt, E. J. Baerends, C. F. Guerra, S. J. A. Van Gisbergen, J. G. Snijders, and T. Ziegler, J. Comput. Chem. 22, 931 (2001).
  33. M. Chabanel, Pure Appl. Chem. 62, 35 (1990).
  34. P. Goralski and M. Chabanel, Inorg. Chem. 26, 2169 (1987).
  35. D. Paoli, M. Lucon, and M. Chabanel, Spectrochim. Acta, Part A 35, 593 (1979).
  36. J. Vaes, M. Chabanel, and M. L. Martin, J. Phys. Chem. 82, 2420 (1978).
  37. P. W. Schultz, G. E. Leroi, and J. F. Harrison, Mol. Phys. 88, 217 (1996).
  38. O. Squalli, M. C. M. Costa, A. Cartier, and M. Chabanel, J. Mol. Struct.: THEOCHEM 109, 11 (1994).
  39. T. J. Chuang and K. B. Eisenthal, J. Chem. Phys. 57, 5094 (1972)JCPSA6000057000012005094000001; [ISI] [CAS]
    B. J. Berne and R. Pecora, Dynamic Light Scattering (Dover, Mineola, 2000).
  40. J. T. Edward, J. Chem. Educ. 47, 261 (1970). [ISI]
  41. M. A. Berg, J. Chem. Phys. 132, 144105 (2010)JCPSA6000132000014144105000001;, M. A. Berg, J. Chem. Phys. 132, 144106 (2010)JCPSA6000132000014144106000001;, K. M. Gaab and C. J. Bardeen, J. Phys. Chem. A 108, 10801 (2004); [Inspec] [CAS]
    K. M. Gaab and C. J. Bardeen, Phys. Rev. Lett. 93, 056001 (2004); [ISI] [MEDLINE]
    S. Garrett-Roe and P. Hamm, Acc. Chem. Res. 42, 1412 (2009);, S. Garrett-Roe, F. Perakis, F. Rao, and P. Hamm, J. Phys. Chem. B 115, 6976 (2011)
    C. Khurmi and M. A. Berg, J. Phys. Chem. A 112, 3364 (2008); [MEDLINE] [CAS]
    E. van Veldhoven, C. Khurmi, X. Z. Zhang, and M. A. Berg, ChemPhysChem 8, 1761 (2007). [MEDLINE]
  42. See supplementary material at http://dx.doi.org/10.1063/1.3665140 for discussion of vibrational peak assignments, LiNCS concentration dependent FTIR spectra, and anisotropy measurements in dimethyl carbonate and ethyl acetate. [EPAPS]

Figures (click on thumbnails to view enlargements)

FIG.1
FTIR spectra of 1.2 M LiNCS in benzonitrile (BN: solid black line) and nitromethane (MeNO2: dashed red line). The peak at ∼2040 cm−1 corresponds to an ion-pair dimer structure with a quadrupole charge distribution (Q-dimer), the peak at ∼2070 cm−1 corresponds to the LiNCS ion pair, and the peak at ∼2100 cm−1 corresponds to the NCS− in a linear ion-pair dimer (L-dimer) that is coordinating two Li+ cations, one with the N atom and the other with the S atom.

FIG.1 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.2
Calculated gas phase structures for the (a) ion pair, (b) linear ion-pair dimer (L-dimer) structure, and (c) ion-pair dimer with a quadrupole charge distribution (Q-dimer). The following atomic color scheme are used: Li, mauve; N, blue; C, black; and S, yellow. The size of the spheres do not reflect the electronic charge density.

FIG.2 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.3
(a) FTIR spectra of benzonitrile (BN: solid black line) and 1.2 M LiNCS in benzonitrile in the region of the CN-stretch of BN (dashed red line). Note the appearance of a blueshifted CN stretch due to direct coordination of Li+ cations by the cyano-group on BN. (b) FTIR spectra of nitromethane (MeNO2: solid black line) and 1.2 M LiNCS in nitromethane (dashed red line) in the region of the symmetric and anti-symmetric nitro-group stretching vibrations. We collected the pure solvent spectra with a 2 μm path length cell and the ionic solution spectra with a 6 μm path length cell. LiNCS causes a slight broadening of the symmetric and anti-symmetric nitro-group stretching vibrations, but we see no spectral evidence for Li+ coordination by MeNO2.

FIG.3 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.4
Logarithmic plot of the time resolved anisotropy for 1.2 M LiNCS in (a) benzonitrile (BN) and (b) nitromethane (MeNO2) measured with polarization selective vibrational pump-probe measurements of the orientational CN stretch of NCS− in the ion pair, Q-dimer, and L-dimer. Note the different time axes for (a) and (b). The solid black lines show the fit of each data set to a tri-exponential decay. The rotational relaxation time constants and amplitudes extracted from the tri-exponential fits can be found in Table 2.

FIG.4 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.5
Early time decay of the anisotropy for the Q-dimer in benzonitrile (BN) and dimethyl carbonate (DMC). The time dependent decay of the anisotropy shows a strongly damped oscillation, with a frequency of ∼18 cm−1 for BN and ∼15 cm−1 for DMC.

FIG.5 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

Supplemental Files (EPAPS)

Tables

Table I. Experimental and calculated absorption peak frequencies, and van der Waals volumes40 of LiNCS ion pair, quadrupole ion-pair dimer (Q-dimer), and linear ion-pair dimer (L-dimer) in MeNO2.

View Table
Table II. Parameters extracted from the fit of the anisotropy data to a bi-exponential decay function: r(t) = A1e−t/τor1+A2e−t/τor2+A3e−t/τor3. The amplitudes have errors of 10% or less.

View Table

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