First row transition metals decorated boron phosphide nanoclusters as nonlinear optical materials with high thermodynamic stability and enhanced electronic properties; A detailed quantum chemical study

Electronic as well as nonlinear optical properties (first hyperpolarizabilities) of boron phosphide nanoclusters doped with first row transition metals (Sc-Zn) are explored using density functional theory (DFT) calculations. Four different doping sites (b(64), b(66), r(4), and r(6)) of the B12P12 nanocluster are considered for doping of the transition metals. Computational results revealed that these transition metals doped boron phosphide complexes are highly stable, and their HOMO-LUMO energy gaps are considerably reduced as compared to the pristine B12P12 nanocage. The highest interaction energy (-74.42 kcal mol(-1)) is observed for Ni@r(4)-B12P12 complex. The lowest HOMO-LUMO energy gap (1.44 eV) is computed for Sc@b(64)-B12P12 complex. Moreover, adsorption of the first row transition metals (Sc-Zn) on the surface of B12P12 nanocluster significantly enhanced the non-linear optical response of the resultant complexes. The highest static first hyperpolarizability value (4.4 x 10(4) au) is computed for Sc@r(4)-B12P12 complex. Moreover, frequency dependent hyperpolarizability calculations are also performed to evaluate the practicality of the transition metal doped boron phosphide (M@B12P12) complexes. The highest electro-optical Pockels effect (EOPE) value of 4.4 x 10(5) au is computed for Sc@r(4)-B12P12 complex while Sc@r(6)-B12P12 gives the highest second harmonic generation (SHG) value of 1.1 x 10(5) au. This study will be advantageous for providing guidance in further designing of new high-performance nonlinear optical (NLO) materials.

Automated summary

The study explores the electronic and nonlinear optical properties of boron phosphide nanoclusters doped with first row transition metals using density functional theory calculations. Transition metals doped boron phosphide complexes are found to be stable with reduced HOMO-LUMO energy gaps. Different doping sites and transition metals have varying effects on the properties of the complexes.