Size dependence of second-order hyperpolarizability of finite periodic chain under Su-Schrieffer-Heeger model

The second hyperpolarizability $\gamma_N(-3\omega\omega,\omega,\omega)$ of $N$ double-bond finite chain of trans-polyactylene is analyzed using the Su-Schrieffer-Heeger model to explain qualitative features of the size-dependence behavior of $\gamma_N$. Our study shows that $\gamma_N/N$ is {\it nonmonotonic} with $N$ and that the nonmonotonicity is caused by the dominant contribution of the intraband transition to $\gamma_N$ in polyenes. Several important physical effects are discussed to reduce quantitative discrepancies between experimental and our results