Theoretical Study on the Static (Hyper)‎Polarizabilities of α-t-Bu-ω-CN-Poly(methylphenyl)‎silane

Abstract EN

The static linear and nonlinear optical properties of the σ-conjugated polymer α-t-Bu-ω-CN-poly(methylphenyl)silane (PMS) are studied at the Coupled-Perturbed Hartree-Fock (CPHF) level with 6-31+G(d) basis set.

The calculated results reveal that the static first hyperpolarizabilities of this system increase with the main chain length and have a good agreement with experiments.

The (hyper)polarizabilities per unit cell have been extrapolated to infinite chain limit and a comparison is made to those of polysilane and polyacetylene (PA).

Besides, other structural properties depending on the σ-conjugated Si–Si skeleton length are investigated as well.

Electron correlation effect is estimated and it turns out that the MP2 static first hyperpolarizability is about 1.5~2.0 times larger than the corresponding CPHF value for the polymer with n≤6.