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Journal of Chemical Physics / Volume 125 / Issue 3 / ARTICLES / Polymers, Biopolymers, and Complex Systems

J. Chem. Phys. 125, 034904 (2006); http://dx.doi.org/10.1063/1.2208356 (14 pages)

Molecular dynamics and interactions of aqueous and dichloromethane solutions of polyvinylpyrrolidone

Hideaki Shirota and Edward W. Castner

Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854-8087

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(Received 27 February 2006; accepted 3 May 2006; published online 19 July 2006)

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

Article Outline

  1. INTRODUCTION
  2. EXPERIMENT AND CALCULATION
  3. RESULTS
    1. Picosecond reorientational dynamics
    2. Femtosecond vibrational dynamics
    3. Density functional theory calculations
  4. DISCUSSION
    1. Reorientational dynamics on the picosecond time scale
    2. Inter- and intramolecular vibrational dynamics
      1. Comparison between polymer and model monomer solutions
      2. Polymer concentration dependence
      3. Comparison between PVP in H2O and CH2Cl2
  5. CONCLUSIONS

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KEYWORDS and PACS

Keywords

polymer solutions, high-speed optical techniques, Raman spectra, optical Kerr effect, hydrogen bonds, vibrational modes

PACS

  • 78.30.C-

    Liquids

  • 78.47.-p

    Spectroscopy of solid state dynamics

  • 61.25.H-

    Macromolecular and polymers solutions; polymer melts

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.2208356

PUBLICATION DATA

ISSN

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

Publisher

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

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