Investigating solvent effects on aggregation behaviour, linear and nonlinear optical properties of silver nanoclusters

We herein report the solvent effects on the aggregation, linear and nonlinear optical properties of silver nanoclusters synthesised using three solvents namely; ethanol, acetone and isopropanol. The Ag clusters were characterized using UV–Visible (UV–vis) and photoluminescence (PL) spectroscopy, Fourier transform-infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), small angle X-ray scattering (SAXS), dynamic light scattering (DLS), and open aperture Z-Scan measurements. Density functional theory (DFT) calculations at the B3PW91 level of theory, were done to compute the electric dipole, quadrupole, octapole and hexadecapole moment of mercaptosuccinic acid and mercaptosuccinic acid-Ag₉ cluster in three solvents. Linear optical properties show characteristic absorption profile with quantum confinement at different wavelengths for all the three clusters. The Open aperture Z-scan measurement in Ag clusters establishes the optical limiting properties which arise mostly from excited state absorption (ESA) and relatively weak saturable absorption (SA). The nonlinear optical behaviour varies within the three clusters with maximum optical limiting value obtained for the clusters synthesised using acetone. The theoretically computed hyperpolarizabilities together with z-scan measurements establish the solvent effect on the clusters and their potential applications in optical limiting devices.