Phosphorus clusters have broadband optical responses, adjustable geometries, and electronic structures, potentially balancing transparency and nonlinearity. In this study, the optical properties of phosphorus clusters are analyzed by using first-principles calculations. Phosphorus clusters exhibit strong light absorption in the ultraviolet region while remaining transparent in the visible to far-infrared bands. Importantly, the third-order nonlinear optical performance of phosphorus clusters surpasses that of p-nitroaniline with a D−π−A structure. The analysis reveals that lone pair electrons with weak nuclear binding induce sensitive nonlinear optical responses of phosphorus clusters. Furthermore, a practical approach for enhancing nonlinear optical effects in a medium via atom replacement and its application to hydride systems are discussed. Lone pair electron materials provide an alternative to conventional organic π-conjugated molecules for nonlinear optical devices, while potentially achieving a better trade-off of nonlinearity versus transparency. This study provides a novel concept for the development of high-performance nonlinear optical materials.
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