Abstract
Ab initio computational chemistry methods have been used to study the molecular structure of polymeric materials. We present here theoretical results for the barriers to internal rotation in several Polyalkylmethacrylate polymers. We also include the results of independent investigations of the backbone and side chain conformations. Our calculations quantitatively reproduce the experimentally determined relaxation energies. It appears that the original experimental assignments are not correct. However, our theoretical predictions are in agreement with the results of new sophisticated temperature dependent NMR experiments.
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References
E. Helfand, Z.R. Wasserman, and T.A. Weber, Macromolecules13,526 (1980);
J. Skolnik and E. Helfand, J. Chem. Phys. 72, 5489 (1980) see for example “Computer Modeling of Matter”, edited by Peter Lykos, ACS Symp. Ser.86 (American Chemical Society, Washington, D.C. 1978), chapters 11 and 12 and references contained therein.
J.A. Pople, “A Priori Geometry Predictions”, in “Applications of Electronic Structure Theory”, H.F. Schaefer III, ed., Plenum Press N.Y. 1977.
P.W. Payne and L.C. Allen, ”Barriers to Rotation and Inversion”, ibid.
A. Karpfen and A. Beyer,J. Comput. Chem. 5, 11 (1984).
P. Pulay,“Methods of Electronic Structure Theory”, ed. H.F. Schaefer III, Plenum Press, N.Y. 1977.
P. Pulay, G. Fogarasi, F. Pang, and J.E. Boggs, J. Amer. Chem. Soc.101, 2550 (1979).
P. Pulay, G. Fogarasi, F. Pang, and J.E. Boggs; J. Chem. Phys.74, 3999 (1981) and references contained therein.
A. Komornicki, K. Ishida, K. Morokuraa, R. Ditchfield, and M. Conrad, Chem. Phys. Lett.,45, 595 (1977).
J.W.McIver Jr. and A. Komornicki, Chem. Phys. Lett.,10, 303 (1971).
W.H. Fink and L.C. Allen,J. Chem. Phys. 46, 2261 (1967).
W.H. Fink and L.C. Allen, ibid.,46, 3270 (1967).
W.H. Fink and L.C. Allen, ibid.,46, 3941 (1967).
L. Pedersen and K. Morokuma ibid.,46, 3941 (1967).
J.R. Hoyland, J. Chem. Phys. 49, 1908 (1968).
J.R. Hoyland, ibid.49, 2563 (1968).
J.R. Hoyland, ibid.50, 2775 (1968).
GRADSCF is an Ab-initio gradient program system designed and written by A. Komornicki at Polyatomics Research and supported on grants through NASA.
B.C. Laskowski, R.L. Jaffe and A. Komornicki, “Conformational Properties, torsional potential and Vibrational Force Field for Methacryloyl Fluoride: An Ab Initio Investigation”, J. Chem. Phys. 82, 5089 (1985).
J.R. Durig, P.A. Brietic and J.S. Church,J. Chem. Phys. 76, 1723 (1982).
N.G. McCrum, B.E. Read, G. Williams,“Anelastic and Dielectric Effects in Polymer Solids”, New York 1967, Chapt. 8.
W.J. Hehre, R.F. Stewart and J.A. Pople,J. Chem. Phys. 51, 1657 (1969)
M.D. Newton, W.A. Lathan, W. J. Hehre and J.A. Pople, ibid.52, 4064 (1970)
R. Ditchfield, W.J. Hehre and J.A. Pople,J. Chem. Phys. 54, 724 (1971).
P.C. Hariharan and J.A. Pople,Mol. Phys., 27, 209 (1974).
T. Miyazawa, Bull. Chem. Soc. Jap. 34, 691 (1961)
N.L. Allinger and S. Profeta, Jr., J. Comp. Chem. 1, 181 (1980).
J.A. Dorsey and B.K. Rao, Macromolecules14, 1575 (1981).
T. Tetsutani, M. Kakizaki and T. Hideshima,Polymer J. 14, 305 (1982).
S-D. Hong, S.Y. Chung, R.F. Fedors and J. Moacanin,J. Polymer Sci; Polymer Physics Ed.21, 1647 (1983).
Encyclopedia of Polymer Science and Technology, (Interscience, New York, 1964), vols. 3–4.
A Gupta, private communication.
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© 1986 D. Reidel Publishing Company
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Laskowski, B.C., Jaffe, R.L., Komornicki, A. (1986). Theoretical Study of the Conformational Properties and Torsional Potential Functions of Polyalkylmethacrylate Polymers. In: Smith, V.H., Schaefer, H.F., Morokuma, K. (eds) Applied Quantum Chemistry. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4746-7_22
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DOI: https://doi.org/10.1007/978-94-009-4746-7_22
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