DFT studies on structural stability, vibrational and linear and nonlinear optical properties of low-dimensional zinc sulfide: from the 3D bulk to the 2D monolayer and the 1D zigzag single-walled nanotubes

Abstract

Abstract Through first-principles calculations, we investigate structural stability, vibrational and linear and nonlinear optical properties of the zinc sulfide (ZnS) in different periodic forms ranging from the 3D bulk to the 2D hexagonal monolayer and their corresponding 1D zigzag single-walled nanotubes. To first order, the electronic wave function on the ground state was constructed using linear combinations of Gaussian-type functions at the DFT/B3LYP level. Then, the Raman and IR spectrum is computed by adopting a Coupled-Perturbed-Hartree–Fock/Kohn–Sham (CPHF/KS) approach. Cohesive, relaxation, and rolling energies, elastic and piezoelectric constants, electronic and nuclear contributions to the polarizability tensor, and nonlinear first and second-order hyperpolarizability tensor components are reported. Our study shows that 3D and 2D forms are stable and show semiconducting behavior, good piezoelectric responses, and fascinating linear and nonlinear optical properties. For 1D single-walled nanotubes, dynamic stability is observed only for the smallest (6,0) nanotubes. For n > 6, imaginary mode frequencies in the simulated IR and Raman spectra indicate dynamic instability. A scanning mode procedure along the largest imaginary vibrational mode is applied in order to determine the stable structures of the largest (14,0), (18,0) and (22,0) ZnS nanotubes. After that, no more imaginary phonon frequencies are detected in their vibrational spectra. Their potential energy surface contains two minima between a saddle point corresponding to a slightly distorted nanotube structure. Our study proves that the zinc sulfide nanostructures possess diverse physical properties so useful for potential applications in nanoelectronics and for nanodevices.