First-principles study of (75)As NQR in arsenic-chalcogenide compounds.

We present a theoretical study of the nuclear quadrupole interaction, ν(Q), of (75)As in crystalline and amorphous materials containing sulfur and selenium, and compare them with experiment. We studied a combination of hydrogen-terminated molecular clusters and periodic cells at various levels of quantum chemical theory. The results show clearly that the standard density functional theory (DFT) approximations, LDA and GGA, underestimate the nuclear quadrupole (NQR) interaction systematically, while Hartree-Fock theory overestimates it to an even greater degree. However, various levels of configuration interaction and the B3LYP hybrid exchange-correlation functional, which includes some exact exchange, give very good quantitative agreement for As bonded only to the chalcogen species. As-As bonds require highly converged basis sets. We have performed a systematic study of the effect of local distortions around an arsenic atom on ν(Q) and η. Using a simple, semiclassical model, we have combined our total energy results with our NQR calculations to predict ν(Q) lineshapes for bond angle and bond length distortions. Our predictions for lineshape, including first and second moments, are in excellent agreement with the results of Su et al for a-As(2)S(3), a-As(2)Se(3) and a-AsSe. We offer new insight into the distortions that led to this inhomogeneous broadening. Our results show clearly that, for trivalent arsenic atoms with zero or one arsenic nearest neighbor, symmetric bond stretching is the predominant contributor to the ν(Q) linewidth. However, in the presence of two arsenic nearest neighbors, distortions of the As-As-As apex angle dominates and, in fact, leads to a much larger second moment, in agreement with experiment.