Theoretical study on the second hyperpolarizabllltles of tetrathlafulvalene (TTF) and tetrathlapentalene (TTP) using highly correlated ab Inltio MO and the density functional theory methods

摘要

We investigate the static second hyperpolarizabilities (gamma) of tetrathiafulvalene (TTF) and tetrathiapentalene (TTP) using the ab initio molecular orbital (MO) method. The cationic radical states of these systems (TTF" and TTP~(+deg) are expected to have large negative y values, which are rare in organic systems, based on our classification rale of y. It turns out that at the higher-order electron correlation level TTP~(+deg) gives a large negative y value though TTF~(+S) gives a positive y. We also investigate the applicability of the density functional theory (DFT) methods to the calculation of the gamma values for these systems. By tuning the mixing parameter of DFT/HF exchange term, a DFT method turns out to semiquantitatively reproduce the y values of TTP and TTP~(+deg) at the higher-order electron correlation method, i.e., CCSD(T), while fail in reproducing the y value of TTF~(+deg). This suggests the necessity of further improvement in correlation functional for obtaining reliable gamma values of charged radical states.