Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
Search:
   
 
 
 
Previous Article
Nematic-fluid structure in wall-field geometry. II. The direct correlation function
An explicit expression for the wall-nematic direct correlation function (DCF) is obtained for any orientation of the wall with respect to an external orienting field. It is found that inside the surfa...
Next Article
Polymer brushes in cylindrical pores: Simulation versus scaling theory
The structure of flexible polymers endgrafted in cylindrical pores of diameter D is studied as a function of chain length N and grafting density , assuming good solvent conditions. A phenomenological ...

Molecular dynamics and interactions of aqueous and dichloromethane solutions of polyvinylpyrrolidone

J. Chem. Phys. 125, 034904 (2006); doi:10.1063/1.2208356

Published 19 July 2006

You are not logged in to this journal. Log in

Hideaki Shirota and Edward W. Castner, Jr.
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854-8087
We have investigated the dynamics of polyvinylpyrrolidone solutions (PVP, Mw=10  000) on time scales from 20  fs  to  42  ps using femtosecond optically heterodyne-detected Raman-induced Kerr effect spectroscopy. To compare the dynamics of polymer solutions with those of the analogous monomer, we also characterized solutions of 1-ethyl-2-pyrrolidone (EP). Dynamics of both PVP and EP solutions have been characterized for sample concentrations of 6.4, 12.7, 24.5, 33.3, and 40.7  wt  %. The longest time scale relaxations observed in the Kerr transients for these solutions occur on the picosecond time scale and are best fit to triexponential functions. The intermediate and slow relaxation time constants for PVP and EP solutions are concentration dependent. The time constants for the PVP solutions are not consistent with the predictions of hydrodynamic models, while the analogous time constants for the EP solutions do display hydrodynamic scaling. The predominant relaxation of the polymer is assigned to reorientations of the pyrrolidone side group or torsional motions of the constitutional repeat unit, with additional relaxation pathways including hydrogen bond reorganization in aqueous solution and segmental motion of multiple repeat units. The vibrational dynamics of PVP and EP solutions occur on the femtosecond time scale. These dynamics are analyzed with a focus on the additional degrees of freedom experienced by EP relative to PVP that result from the absence of the tether from the pyrrolidone group on the main chain backbone. The intermolecular Kerr spectra of PVP in H2O and CH2Cl2 differ because H2O can donate a hydrogen bond to the carbonyl acceptor group on the pyrrolidone ring, while CH2Cl2 cannot. ©2006 American Institute of Physics
History: Received 27 February 2006; accepted 3 May 2006; published 19 July 2006
Permalink: http://link.aip.org/link/?JCPSA6/125/034904/1
BUY THIS ARTICLE   (US$24)
Download HTML Download Sectioned HTML Download PDF (1536 kB) View Cart

EPAPS

KEYWORDS and PACS

Keywords
PACS
  • 78.30.Cp
    Infrared and Raman spectra in liquids
  • 78.47.+p
    Time-resolved optical spectroscopies and other ultrafast optical measurements in condensed matter
  • 61.25.Hq
    Structure of macromolecular and polymer solutions, and polymer melts; swelling
  • YEAR: 2006

RELATED DATABASES


To view database links for this article,
you need to log in.
To view database links for this article,
you need to log in.

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (98)
View in Separate Window/Tab
For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. B. Nair, Int. J. Toxicol. 17, 95 (1998).
  2. J. H. Guo, G. W. Skinner, W. W. Harcum, and P. E. Barnum, Pharm. Sci. Technol. Today 1, 254 (1998).
  3. M. Kurata and W. H. Stockmayer, Adv. Polym. Sci. 3, 196 (1963).
  4. Polymer Handbook, edited by J. Brandrup, E. H. Inmergut, and E. A. Grulke (Wiley, New York, 1999).
  5. P. J. Flory, Principles of Polymer Chemistry (Cornell University Press, Ithaca, 1953).
  6. P. D. de Gennes, Scaling Concepts in Polymer Physics (Cornell University Press, Ithaca, 1979).
  7. M. Doi and S. F. Edwards, The Theory of Polymer Dynamics (Oxford University Press, Oxford, 1986).
  8. S. Matsuoka, Relaxation Phenomena in Polymers (Carl Hanser Verlag, Munich, 1992).
  9. M. D. Ediger and D. B. Adolf, Adv. Polym. Sci. 116, 73 (1994).
  10. B. Ewen and D. Richter, Adv. Polym. Sci. 134, 1 (1997).
  11. D. McMorrow, W. T. Lotshaw, and G. A. Kenney-Wallace, IEEE J. Quantum Electron. 24, 443 (1988).
  12. W. T. Lotshaw, D. McMorrow, N. Thantu, J. S. Melinger, and R. Kitchenham, J. Raman Spectrosc. 26, 571 (1995).
  13. S. Kinoshita, Y. Kai, T. Ariyoshi, and Y. Shimada, Int. J. Mod. Phys. B 10, 1229 (1996).
  14. E. W. Castner and M. Maroncelli, J. Mol. Liq. 77, 1 (1998).
  15. N. A. Smith and S. R. Meech, Int. Rev. Phys. Chem. 21, 75 (2002).
  16. B. J. Loughnane, R. A. Farrer, A. Scodinu, T. Reilly, and J. T. Fourkas, J. Phys. Chem. B 104, 5421 (2000).
  17. R. A. Farrer and J. T. Fourkas, Acc. Chem. Res. 36, 605 (2003).
  18. A. Scodinu and J. T. Fourkas, J. Phys. Chem. B 106, 10292 (2002).
  19. X. Zhu, R. A. Farrer, and J. T. Fourkas, J. Phys. Chem. B 109, 12724 (2005).
  20. N. T. Hunt, A. A. Jaye, and S. R. Meech, J. Phys. Chem. B 107, 3405 (2003).
  21. N. T. Hunt, A. A. Jaye, and S. R. Meech, Chem. Phys. Lett. 371, 304 (2003).
  22. N. T. Hunt, A. A. Jaye, A. Hellman, and S. R. Meech, J. Phys. Chem. B 108, 100 (2004).
  23. A. A. Jaye, N. T. Hunt, and S. R. Meech, Langmuir 21, 1238 (2005).
  24. G. Giraud and K. Wynne, J. Am. Chem. Soc. 124, 12110 (2002).
  25. G. Giraud, J. Karolin, and K. Wynne, Biophys. J. 85, 1903 (2003).
  26. J. D. Eaves, C. J. Fecko, A. L. Stevens, P. Peng, and A. Tokmakoff, Chem. Phys. Lett. 376, 20 (2003).
  27. S. D. Gottke, D. D. Brace, H. Cang, B. Bagchi, and M. D. Fayer, J. Chem. Phys. 116, 360 (2002).
  28. H. Cang, J. Li, V. N. Novikov, and M. D. Fayer, J. Chem. Phys. 119, 10421 (2003).
  29. H. Cang, J. Li, V. N. Novikov, and M. D. Fayer, J. Chem. Phys. 118, 9303 (2003).
  30. J. Li, I. Wang, and M. D. Fayer, J. Phys. Chem. B 109, 6514 (2005).
  31. J. Li, H. Cang, H. C. Andersen, and M. D. Fayer, J. Chem. Phys. 124, 014902 (2006).
  32. B. R. Hyun and E. L. Quitevis, Chem. Phys. Lett. 370, 725 (2003).
  33. B. R. Hyun and E. L. Quitevis, Chem. Phys. Lett. 373, 526 (2003).
  34. N. T. Hunt and S. R. Meech, J. Chem. Phys. 120, 10828 (2004).
  35. B. R. Hyun, S. V. Dzyuba, R. A. Bartsch, and E. L. Quitevis, J. Phys. Chem. A 106, 7579 (2002).
  36. J. R. Rajian, S. F. Li, R. A. Bartsch, and E. L. Quitevis, Chem. Phys. Lett. 393, 372 (2004).
  37. G. Giraud, C. M. Gordon, I. R. Dunkin, and K. Wynne, J. Chem. Phys. 119, 464 (2003).
  38. H. Cang, J. Li, and M. D. Fayer, J. Chem. Phys. 119, 13017 (2003).
  39. H. Shirota, A. M. Funston, J. F. Wishart, and E. W. Castner, Jr., J. Chem. Phys. 122, 184512 (2005).
  40. H. Shirota and E. W. Castner Jr., J. Phys. Chem. A 109, 9388 (2005).
  41. H. Shirota and E. W. Castner Jr., J. Phys. Chem. B 109, 21576 (2005).
  42. A. Sengupta, M. Terazima, and M. D. Fayer, J. Phys. Chem. 96, 8619 (1992).
  43. A. Sengupta and M. D. Fayer, J. Chem. Phys. 100, 1673 (1994).
  44. H. Shirota and E. W. Castner, Jr., J. Am. Chem. Soc. 123, 12877 (2001).
  45. H. Shirota, J. Phys. Chem. B 109, 7053 (2005).
  46. N. T. Hunt and S. R. Meech, Chem. Phys. Lett. 400, 368 (2004).
  47. H. Shirota, J. Chem. Phys. 122, 044514 (2005).
  48. D. McMorrow and W. T. Lotshaw, J. Phys. Chem. 95, 10395 (1991).
  49. P. P. Wiewior, H. Shirota, and E. W. Castner, Jr., J. Chem. Phys. 116, 4643 (2002).
  50. M. J. Frisch et al., GAUSSIAN 03, Gaussian Inc., Pittsburgh, PA, 2003.
  51. A. D. Becke, J. Chem. Phys. 98, 5648 (1993).
  52. C. Lee, W. Yang, and R. G. Parr, Phys. Rev. B 37, 785 (1988).
  53. P. E. Rouse Jr., J. Chem. Phys. 21, 1272 (1953).
  54. B. H. Zimm, J. Chem. Phys. 24, 269 (1956).
  55. D. McMorrow and W. T. Lotshaw, Chem. Phys. Lett. 174, 85 (1990).
  56. See EPAPS Document No. E-JCPSA6-124-507623 for the following relevant information: A. Geometries optimized at the B3LYP/6-311++G(d,p) level for ethylpyrrolidone (EP), H2O, CH2Cl2, and a ternary cluster of one EP with two H2O molecules; B. A Comparison between observed intramolecular modes for PVP and EP in both H2O and CH2Cl2 solutions, with the gas-phase calculated normal modes listed for EP. Vibrational displacements for the first nine normal modes are illustrated with arrows; C. The six unique polarizability tensor elements for EP, H2O, and CH2Cl2 are tabulated; and D. The complete bibliographic citation for Ref. 50, to GAUSSIAN 03, is listed. This document can be reached via a direct link in the online article's HTML reference section or via the EPAPS homepage (http://www.aip.org/pubservs/epaps.html). [EPAPS]
  57. Y. Tanimura and S. Mukamel, J. Chem. Phys. 99, 9496 (1993).
  58. S. Mukamel, Principles of Nonlinear Optical Spectroscopy (Oxford University Press, New York, 1995).
  59. D. A. Long, The Raman Effect (Wiley, West Sussex, 2002).
  60. J. T. Edward, J. Chem. Educ. 47, 261 (1970).
  61. D. Kivelson and P. A. Madden, Annu. Rev. Phys. Chem. 31, 523 (1980).
  62. J. L. Dote, D. Kivelson, and R. N. Schwartz, J. Phys. Chem. 85, 2169 (1981).
  63. G. R. Fleming, Chemical Applications of Ultrafast Spectroscopy (Oxford University Press, New York, 1986).
  64. B. J. Berne and R. Pecora, Dynamic Light Scattering: With Applications to Chemistry, Biology, and Physics (Dover, Mineola, NY, 2000).
  65. We have recently observed an extra slow relaxation component (about 66  ps) with the small amplitude for aqueous polyacrylamide solution with the concentration of about 20  wt  % by a better signal-to-noise ratio quality and time resolution femtosecond OHD-RIKES system (Ref. 80).
  66. S. Sen, D. Sukul, P. Dutta, and K. Bhattacharyya, J. Phys. Chem. B 106, 3763 (2002).
  67. A. Datta, S. Das, D. Mandal, S. K. Pal, and K. Bhattacharyya, Langmuir 13, 6922 (1997).
  68. P. A. Madden and T. I. Cox, Mol. Phys. 43, 287 (1981).
  69. P. A. Madden, in Molecular Liquids: Dynamics and Interactions, edited by J. Yarwood (Reidel, Dordrecht, 1984), p. 431.
  70. L. C. Geiger and B. M. Ladanyi, J. Chem. Phys. 89, 6588 (1988).
  71. L. C. Geiger and B. M. Ladanyi, Chem. Phys. Lett. 159, 413 (1989).
  72. M. Cho, G. R. Fleming, S. Saito, I. Ohmine, and R. M. Stratt, J. Chem. Phys. 100, 6672 (1994).
  73. R. M. Stratt, Acc. Chem. Res. 28, 201 (1995).
  74. I. Ohmine and S. Saito, Acc. Chem. Res. 32, 741 (1999).
  75. R. L. Murry, J. T. Fourkas, and T. Keyes, J. Chem. Phys. 109, 2814 (1998).
  76. S. Ryu and R. M. Stratt, J. Phys. Chem. B 108, 6782 (2004).
  77. G. Tao and R. M. Stratt, J. Phys. Chem. B 110, 976 (2006).
  78. M. T. Sonoda, S. M. Vechi, and M. S. Skaf, Phys. Chem. Chem. Phys. 7, 1176 (2005).
  79. M. D. Elola, B. M. Ladanyi, A. Scodinu, B. J. Loughnane, and J. T. Fourkas, J. Phys. Chem. B 109, 24085 (2005).
  80. H. Shirota and H. Ushiyama (unpublished).
  81. G. E. Walrafen, in Water: A Comprehensive Treatise Vol. 1: The Physics and Physical Chemistry of Water, edited by F. Franks (Plenum, New York, 1972), Chap. 5.
  82. G. E. Walrafen, Y. C. Chu, and G. J. Piermarini, J. Phys. Chem. 100, 10363 (1996).
  83. C. J. Fecko, J. J. Loparo, S. T. Roberts, and A. Tokmakoff, J. Chem. Phys. 122, 054506 (2005).
  84. S. Palese, L. Schilling, R. J. D. Miller, P. R. Staver, and W. T. Lotshaw, J. Phys. Chem. 98, 6308 (1994).
  85. S. Palese, J. T. Buontempo, L. Schilling, W. T. Lotshaw, Y. Tanimura, S. Mukamel, and R. J. D. Miller, J. Phys. Chem. 98, 12466 (1994).
  86. S. Palese, S. Mukamel, R. J. D. Miller, and W. T. Lotshaw, J. Phys. Chem. 100, 10380 (1996).
  87. Y. J. Chang and E. W. Castner, Jr., J. Chem. Phys. 99, 7289 (1993).
  88. Y. J. Chang and E. W. Castner, Jr., J. Chem. Phys. 99, 113 (1993).
  89. Y. J. Chang and E. W. Castner, J. Phys. Chem. 98, 9712 (1994).
  90. E. W. Castner, Y. J. Chang, Y. C. Chu, and G. E. Walrafen, J. Chem. Phys. 102, 653 (1995).
  91. H. Shirota, K. Yoshihara, N. A. Smith, S. J. Lin, and S. R. Meech, Chem. Phys. Lett. 281, 27 (1997).
  92. A. A. Jaye, N. T. Hunt, and S. R. Meech, J. Chem. Phys. 124, 024506 (2006).
  93. K. Winkler, J. Lindner, H. Bursing, and P. Vohringer, J. Chem. Phys. 113, 4674 (2000).
  94. K. Winkler, J. Lindner, and P. Vohringer, Phys. Chem. Chem. Phys. 4, 2144 (2002).
  95. C. J. Fecko, J. D. Eaves, and A. Tokmakoff, J. Chem. Phys. 117, 1139 (2002).
  96. N. T. Hunt, A. R. Turner, and K. Wynne, J. Phys. Chem. B 109, 19008 (2005).
  97. A. Idrissi, P. Bartolini, M. Ricci, and R. Righini, J. Chem. Phys. 114, 6774 (2001).
  98. A. Idrissi, P. Bartolini, M. Ricci, and R. Righini, Phys. Chem. Chem. Phys. 5, 4666 (2003).

CITING ARTICLES
For access to citing articles, you need to log in.
For access to citing articles, you need to Log in.


Copyright © American Institute of Physics