A New Strategy of bi-Alkali Metal Doping to Design Boron Phosphide Nanocages of High Nonlinear Optical Response with Better Thermodynamic Stability

Nonlinear optical materials have gained immense scientific interest in the recent times owing to their vast applications in various fields. Continuous strides are made to design and synthesize materials with large nonlinear optical response and high thermodynamic stability. In this regard, we present here bi-alkali metal doping on boron phosphide nanocage as a new strategy to design thermodynamically stable materials with large nonlinear optical response. The geometric, thermodynamic, electronic, optical and nonlinear optical properties of complexes are explored through density functional theory (DFT) simulations. The doping of alkali metal atoms introduces excess of electrons in the host (B 12 P 12 ) nanocage. These electrons contribute towards the formation of new HOMOs, which reduce the HOMO–LUMO gaps of the designed complexes. The HOMO–LUMO gaps of the designed complexes range from 0.63 eV to 3.69 eV. The diffused excess electrons also induce large hyperpolarizability values in the complexes i.e. up to 4.0 × 10 4 au. TD-DFT calculations have been performed for crucial transition states and UV–VIS analysis. Non-covalent interaction (NCI) along with quantum theory of the atoms in molecules (QTAIM) analyses are carried out to understand the bonding interactions between alkali metal atoms and B 12 P 12 nanocage. All the obtained results suggest that bi-alkali metal doped nanocages are exceptionally stable materials with improved NLO response.