Theoretical study on nonlinear optical properties of the Li+[calix[4]pyrrole]Li−dimer, trimer and its polymer with diffuse excess electrons

The static (hyper)polarizabilities of the dimer and trimer with diffuse excess electrons, [Li+[calix[4]pyrrole]Li−]n, are firstly investigated by the DFT(B3LYP) method in detail. For the dimer and trimer, a Li atom inside each calix[4]pyrrole unit is ionized to form a diffuse excess electron. The results show that the dimer and trimer containing two and three excess electrons, respectively, have very large first hyperpolarizablities as 2.3 × 104 and 4.0 × 104 au, which are 30 and 40 times larger than that of the corresponding [calix[4]pyrrole]n (n = 2, 3) without Li atom. Also, β values of dimer and trimer are twice and four times as large as that of monomer containing one excess electron. Obviously, not only excess electron but also the number of excess electron plays an important role in increasing the first hyperpolarizability. Moreover, the (hyper)polarizabilities of the [Li+[calix[4]pyrrole]Li−]n polymer are investigated at ab initio level by using the elongation finite‐field (elongation FF) method. All the oligomers of the [Li+[calix[4]pyrrole]Li−]n with many excess electrons exhibit very large first hyperpolarizability and large second hyperpolarizability. The present investigation shows that by introducing several and more excess electrons into the nonlinear optical (NLO) materials will be an important strategy for improving their NLO properties, which will be helpful for design of NLO materials. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010