Substitution effects on the polarizability (α) and first hyperpolarizability (β) of all-trans hexatriene

Abstract

Polarizability (α) and first hyperpolarizability (β) have been calculated for a set of substituted all-trans hexatriene NO2-linker-D compounds at TDHF and CPHF/6-31+G∗ levels of theory. Effects due to the nature of D/A pair type on the geometrical structural and the electrical proprieties are investigated. It turns out that electronics polarizability and first hyperpolarizability are considerably intensified by the functionality of amino groups, as well the pair NO2/NEt2 associated the greatest α and β values. The relationships between βe and βv are investigated and for molecules with N heteroatom at the donor groups considered the βLv(0)/ βLe(0) ratio lies in the range 1.04–1.36. Although the level of theory employed herein gives significantly different results only for the vibrational, longitudinal hyperpolarizability counterpart than those obtained by Bishop et al. (1998) at the RHF level, the overall conclusions remain unchanged. For both static and dynamic polarizabilities values an excellent agreement between the CPHF, TDHF and PM6 results, they give a correlation coefficient of 0.96 and 0.95, respectively. The frequency and solvent effect were also considered.