Nonlinear optical properties of polydiacetylene with donor-acceptor substitution block

The elongation finite-field (elongation-FF) method is applied to donor/acceptor substituted polydiacetylenes (PDAs) for the estimation of substituent effects on nonlinear optical (NLO) properties. The first hyperpolarizability (Β) and the second hyperpolarizability (γ) of PDA with separated donor and acceptor substitution blocks have much larger values than those of the other substituted PDAs. For the PDAs with donor and acceptor substitution blocks, the relationship between the NLO properties and the block period is examined. It is shown, from the local density of states, that γ of a system with a quantum well structure has a maximum value at a certain block size. This indicates that by tuning the size of proper block it is possible to achieve the largest γ value in block polymers. Furthermore, the through-space/bond interaction analysis is performed to examine the π -conjugation effects on the NLO properties for particular substituted PDA. It is demonstrated by our quantitative analysis that Β is affected by electron transfers in the molecule, and the quantum well structure is critical for γ improvement.