Feasibility of density functional methods to predict dielectric properties of polymers
- 14 February 2008
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 128 (6), 064109
- https://doi.org/10.1063/1.2828511
Abstract
Feasibility of density functional theory (DFT) to predict dielectric properties such as polarizability of saturated polymers is investigated. Small saturated molecules, methane and propane, which is a monomer of polypropylene chain, are used in testing the methods. Results for polarizabilities based on several density functionals together with different basis sets are compared and contrasted with each other, with results by Hartree-Fock and second-order Moller-Plesset perturbation theory, as well as experimental data. The generalized gradient approximation PW91 method together with the 6-311++G** basis set is found to be the most suitable method, in terms of sufficient accuracy and computational efficiency, to calculate polarizabilities for large oligomers of polypropylene. The dielectric constant is then determined using the calculated polarizabilities and the Clausius-Mossotti equation. The molecular DFT methods at the PW91/6-311++G** level together with the Clausius-Mossotti equation give dielectric constants for saturated polymers such as polypropylene in good accordance with the experimental values. (C) 2008 American Institute of Physics.Keywords
This publication has 66 references indexed in Scilit:
- Periodic and High-Temperature Disordered Conformations of Polytetrafluoroethylene Chains: An ab Initio ModelingJournal of the American Chemical Society, 2006
- Van der Waals interaction of parallel polymers and nanotubesComputational Materials Science, 2005
- Linear-scaling formation of Kohn-Sham Hamiltonian: Application to the calculation of excitation energies and polarizabilities of large molecular systemsThe Journal of Chemical Physics, 2004
- Basis set and electron correlation effects on initial convergence for vibrational nonlinear optical properties of conjugated organic moleculesThe Journal of Chemical Physics, 2004
- Application of time-dependent current-density-functional theory to nonlocal exchange-correlation effects in polymersThe Journal of Chemical Physics, 2003
- Electron correlation corrected static polarizabilities of polymers with linear and cyclic conjugated elementary cellsThe Journal of Chemical Physics, 2002
- Comparison of local-density and Hartree–Fock calculations of molecular polarizabilities and hyperpolarizabilitiesThe Journal of Chemical Physics, 1993
- Linear and nonlinear polarizabilities of t r a n s-polysilane from a b i n i t i o oligomer calculationsThe Journal of Chemical Physics, 1992
- Ab initio calculations of polarizabilities and second hyperpolarizabilities in organic molecules with extended .pi.-electron conjugationThe Journal of Physical Chemistry, 1989
- Polarizability of polyethyleneMacromolecules, 1987