Vibrational Dynamics and Heat Capacity of Syndiotactic Poly(Methyl Methacrylate)

The normal modes and their dispersion in syndiotactic poly(methyl methacrylate) are obtained using Wilson's GF matrix method as modified by Higgs. Optically active frequencies corresponding to the zone center and zone boundary are identified and discussed. The Urey Bradley potential field is obtained by least square fitting of the observed infrared and Raman bands. Heat capacity was obtained from dispersion curves via density‐of‐states. A comparative study of isotactic and syndiotactic forms of poly(methyl methacrylate) is presented.

[1]  P. W. Higgs.  The vibration spectra of helical molecules: infra-red and Raman selection rules, intensities and approximate frequencies , 1953, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[2]  J. Spĕvác̆ek,et al.  Ordered structures of syndiotactic poly(methyl methacrylates) studied by a combination of infrared, Raman, and NMR spectroscopy. , 1986 .

[3]  S. Krimm,et al.  CO stretch mode splitting in the formic acid dimer: Electrostatic models of the intermonomer interaction , 1987 .

[4]  J. Spĕvác̆ek,et al.  An investigation of the self-aggregation process of syndiotactic poly(methyl methacrylate) in solution by using infrared spectra , 1988 .

[5]  P. Sundararajan.  Conformational analysis of poly(methyl methacrylate) , 1986 .

[6]  J. Koenig,et al.  Assignment of the Carbon-Hydrogen Stretching and Bending Vibrations of Poly(Methyl Methacrylate) by Selective Deuteration , 1979 .

[7]  V. D. Gupta,et al.  Phonon dispersion in helical s(2/1)2 syndiotactic polystyrene , 1995 .

[8]  R. A. Mosher,et al.  Conformational energies of stereoregular poly(methyl methacrylate) by Fourier transform infrared spectroscopy , 1981 .

[9]  G. Challa,et al.  ASSOCIATION OF STEREOREGULAR POLY(METHYL METHACRYLATES) , 1976 .

[10]  H. Tadokoro,et al.  Double Strand Helix of Isotactic Poly(methyl methacrylate , 1976 .

[11]  P. Tandon,et al.  Phonon dispersion and heat capacity in poly(ε-caprolactone) , 2004 .

[12]  J. Dybal,et al.  Vibrational spectra and structure of stereoregular poly(methyl methacrylates) and of the stereocomplex , 1983 .

[13]  S. Krimm,et al.  Normal-mode analysis of infrared and Raman spectra of crystalline isotactic poly(methyl methacrylate) , 1990 .

[14]  G. Challa,et al.  Association of stereoregular poly(methyl methacrylates): 4. Further study on the composition of the stereocomplex , 1979 .

[15]  Anuj Kumar,et al.  Vibrational dynamics and heat capacity of syndiotactic poly(4-methyl-1-pentene) , 2001 .

[16]  S. Krimm,et al.  Transition dipole interaction in polypeptides: Ab initio calculation of transition dipole parameters , 1984 .

[17]  Poonam Sharma,et al.  Vibrational dynamics of syndiotactic poly(1-butene) , 2000 .

[18]  G. Challa,et al.  Association of Stereoregular Poly(methyl methacrylates). 6. Double-Stranded Helical Structure of the Stereocomplex of Isotactic and Syndiotactic Poly(methyl methacrylate) , 1982 .

[19]  H. Nagai.  Infrared spectra of stereoregular polymethyl methacrylate , 1963 .

[20]  P. Flory,et al.  Configurational characteristics of poly(methyl methacrylate) , 1974 .

[21]  S. Krimm,et al.  Intermolecular interaction effects in the amide I vibrations of polypeptides. , 1972, Proceedings of the National Academy of Sciences of the United States of America.

[22]  V. D. Gupta,et al.  Normal vibrations and their dispersion in syndiotactic polystyrene , 1994 .

[23]  Poonam Sharma,et al.  Phonon dispersion in poly(l-arginine) , 2002 .

[24]  S. Krimm,et al.  Vibrational analysis of conformation in peptides, polypeptides, and proteins , 1983, Biopolymers.

[25]  W. Qian,et al.  A spectroscopically effective molecular mechanics model for the intermolecular interactions of the hydrogen-bonded N-methylacetamide dimer , 1999 .

[26]  P. Schmidt,et al.  Stretching and deformation vibrations of CH2, C(CH3) and O(CH3) groups of poly(methyl methacrylate) , 1979 .

[27]  Samuel Krimm,et al.  A new electrostatic model for molecular mechanics force fields , 2000 .

[28]  B. Wunderlich,et al.  On theCp toCv conversion of solid linear macromolecules II , 1989 .

[29]  J. Spĕvác̆ek,et al.  High-resolution carbon-13 nuclear magnetic resonance spectra and structure of amorphous and crystalline forms of stereoregular poly(methyl methacrylate)s , 1990 .

[30]  Yoshihide Higashihata,et al.  Structural change of st-PMMA on drawing, absorption and desorption of solvents , 1982 .

[31]  F. E. Karasz,et al.  Thermodynamic properties of stereoregular poly(methyl methacrylate) , 1982 .

[32]  Donald F. Hornig,et al.  Molecular Vibrations. The Theory of Infrared and Raman Vibrational Spectra. , 1956 .