Abstract
Contrary to the enormous number of previous studies on carbon nanotubes (CNTs), herein, we realized the origin of the intrinsic open-shell diradical character and second hyperpolarizability gamma using a broken symmetry approach. This study was inspired by our recent findings (S. Muhammad, et al., Nanoscale, 2016, 8, 17998 and Nakano, et al., J. Phys. Chem. C, 2016, 120, 1193). We performed structural modifications through a unique asymmetric donor-nanotube framework, which led to a novel paradigm of modified CNTs with tunable open-shell diradical character and remarkably superior NLO response properties. Interestingly, asymmetry and diradical character were found to be the crucial factors to modulate the second hyperpolarizability gamma. We initially performed a comparative analysis of the diradical characters and y amplitudes of boron nitride nanotubes (BNNTs) and CNTs possessing significant ionic characters and covalent characters, respectively. The basic findings for these simple configurations were further extended to the donor-acceptor CNT paradigm, which finally led to excellent asymmetric donor-CNT configurations with remarkably larger gamma amplitudes. Furthermore, among the CNTs, finite length zigzag CNT(6,0)(3) were modified with different donor-acceptor configurations. Interestingly, for the first time, unique donor-nanotube configurations [1,4-(NH2)(2)CNT-(6,0)(3) and 1,4-(NH2)(2) CNT-(6,0)(5)] were found; they showed significantly robust y amplitudes as large as 2519 x 10(3) and 4090 x 10(3) a.u. at the LC-UBLYP (mu = 0.33)/6-31G* level of theory. Additionally, several molecular level insights have been obtained for these novel donor-nanotube configurations using their odd electron densities, molecular electrostatic maps, densities of states and gamma density analyses to highlight the realization of these novel materials for highly efficient optical and NLO applications.