Quantum Chemical Calculation on 1H NMR Chemical Shifts of PMMA/PVPh Blends


Article Preview

Prediction of chemical shifts using quantum chemical calculation is helpful for assigning nuclear magnetic resonance (NMR) spectra, and very important in structure determination. In this paper, we calculated 1H chemical shifts (δH) of poly (methyl methacrylate) (PMMA), poly (4-vinyl phenol) (PVPh) and their polymer blends. Density functional theory (DFT) was used to computeδH of hydroxyl groups (OH) for both PVPh homopolymer and PMMA/PVPh polymer blends. The calculated values forδH of OH groups with or without forming hydrogen bonds agreed reasonably well with the experimental values. It was found that the δH of OH groups moved downfield when they formed hydrogen bonds with both other OH groups and carbonyl groups (C=O). The simulated solid state 1H NMR spectra based on the B3LYP // GIAO method yielded results for the PMMA, PVPh and PMMA/PVPh, showed excellent agreement with the experimental results. It indicates that the 1H NMR spectra are influenced by the main-chain conformations and the hydrogen bond types.



Advanced Materials Research (Volumes 301-303)

Edited by:

Riza Esa and Yanwen Wu






W. G. Fu et al., "Quantum Chemical Calculation on 1H NMR Chemical Shifts of PMMA/PVPh Blends", Advanced Materials Research, Vols. 301-303, pp. 263-268, 2011

Online since:

July 2011




[1] R. Ditchfield . Mol. Phys. , Self-consistent perturbation theory of diamagnetism I. A gauge-invariant LCAO method for N.M.R. chemical shifts, Mol. Phys, vol. 2, 1974, pp.789-807, doi: 10. 1080/00268977400100711.

DOI: 10.1080/00268977400100711

[2] A. J. Beeler , A. M. Orendt, D. M. Grant, P.W. Cutts, J. Michl, K.W. Zilm, et al. Low-temperature carbon-13 magnetic resonance in solids. 3. Linear and pseudolinear molecules, J. Am. Chem. Soc. , vol. 106, 1984, pp.7672-7674.

DOI: 10.1021/ja00337a003

[3] R. E. Wasylishen, S. Wooibroek, J. B. Macdonald. A more reliable oxygen-17 absolute chemical shielding scale, J. Chem. Phys., vol. 81, 1984, pp.1057-1060, doi: 10. 1063/1. 447799.

DOI: 10.1063/1.447799

[4] D. B. Chesnut, C. K. Foley. Some simple basis sets for accurate 13c chemical shift calculations, Chem. Phys. Lett. , vol. 118, 1985, pp.316-321. doi: 10. 1016/0009-2614(85)85323-9.

DOI: 10.1016/0009-2614(85)85323-9

[5] T. A. Keith , R. F. W. Bader. Calculation of magnetic response properties using atoms in molecules, Chem. Phys. Lett. , vol. 194, 1992, pp.1-8, doi: 10. 1016/0009-2614(92)85733-Q.

[6] T. Helgaker, M. Jaszunski, K. Ruud. Chem. Ab initio methods for the calculation of NMR shielding and indirect spin−spin coupling constants, Rev, vol. 99, 1999, pp.293-352, doi: 10. 1021/cr960017t.

DOI: 10.1021/cr960017t

[7] J. Aneta, P. Jaroslaw, R. Stanislaw. DFT study of a novel lead structure in the isoxazole heterocyclic system, J. Mol. Struct. : THEOCHEM, vol. 636, 2003, pp.203-214, doi: 10. 1016/S0166-1280(03)00482-2.

DOI: 10.1016/s0166-1280(03)00482-2

[8] P. Maciej, K. Jerzy, P. Miroslaw, W. Iwona. 1H, 13C NMR studies and GIAO/DFT calculations of substituted N-(4-Aryl-1- piperazinylbut yl) derivatives, new analogues of buspirone, J. Mol. Struct., vol. 698, 2004, pp.93-102.

DOI: 10.1016/j.molstruc.2004.04.026

[9] W. G. Fu, B. L. Li, T.H. Chen, Pingchu Sun, Q. J. Jin, D. T. Ding. Hydrogen bonding interaction, miscibility and dynamics in PMMA/PVPh blends as revealed by advanced multi-scale solid-state NMR, Macromolecules, 2010, unpublished.

[10] M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al. Gaussian 03, Revision C. 02; Gaussian, Inc.: Pittsburgh PA, (2003).

[11] H. F. Hameka. On the magnetic shielding in the hydrogen molecule, Mol. Phys. vol. 1, 1958, pp.203-215.

[12] K. Wolinski, K. J. F. Hilton, P. Pulay Efficient implementation of the Gauge-independent atomic orbital method for NMR chemical shift calculations, J. Am. Chem. Soc. vol., 112, 1990, pp.8251-8282, doi: 10. 1021/ja00179a005.

DOI: 10.1021/ja00179a005

In order to see related information, you need to Login.