Circular dichroism in two-dimensional BC6N and B3C2N3in absence of intervalley excitonic coupling.

Two-dimensional (2D) noncentrosymmetric systems offer potential opportunities for exploiting the valley degrees of freedom for advanced information processing, owing to non-zero Berry curvature. However, such valley polarization in 2D materials is crucially governed by the intervalley excitonic scattering in momentum space due to reduced electronic degrees of freedom and consequent enhanced electronic correlation. Here, we study the valley excitonic properties of two 2D noncentrosymmetric complementary structures, namely, BC6N and B3C2N3using first principles-based GW calculations combined with the Bethe-Salpeter equation, that brings the many-body interactions among the quasiparticles. Thek-resolved oscillator strength of their first bright exciton indicates their ability to exhibit valley polarization under the irradiation of circularly polarized light of different chiralities. Both the systems show significant singlet excitonic binding energies of 0.74 eV and 1.31 eV, respectively. Higher stability of dark triplet excitons as compared to the singlet one can lead to higher quantum efficiency in both the systems. The combination of large excitonic binding energies and the valley polarization ability with minimal intervalley scattering make them promising candidates for applications in advanced optical devices and information storage technologies.

g-B3 C2 N3 : A Potential Two Dimensional Metal-free Photocatalyst for Overall Water Splitting.

Based on hybrid density functional theory (DFT) calculations, we propose a new two-dimensional (2D) B-C-N material, graphitic- B 3 C 2 N 3 ${B_3 C_2 N_3 }$ (g- B 3 C 2 N 3 ${B_3 C_2 N_3 }$ ), with the promising prospect of metal-free photocatalysis. We find it to be a near ultraviolet (UV) absorbing direct band gap (3.69 eV) semiconductor with robust dynamical and mechanical stability. Estimating the band positions with respect to water oxidation and hydrogen reduction potential levels along with a detailed analysis of reaction mechanism of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), we observe that g- B 3 C 2 N 3 ${B_3 C_2 N_3 }$ monolayer can be efficiently used for hydrogen fuel generation over entire pH range as well as for spontaneous water splitting at basic pH range. Upon biaxial strain application, band positions get realigned along with the free energy change that is involved in HER and OER. Consequently, operational range of pH for OER gets broadened and the proposed material exhibits the ability to perform spontaneous and simultaneous oxidation and reduction even in neutral pH. The combination of pH variation and applied strain can be used as a key to control the reducing and/or oxidizing abilities precisely for diverse photocatalytic reactions to attain environmental sustainability.

Antiferromagnetic spin ordering in two-dimensional honeycomb lattice of SiP3.

Magnetism in low-dimensional materials has been of sustained interest due to its intriguing quantum mechanical origin and promising device applications. Here, we propose a buckled honeycomb lattice of stoichiometry SiP3, a two-dimensional binary group-IV and V material that exhibits an antiferromagnetic ground state with itinerant electrons. Here we perform elemental Si substitution in pristine blue phosphorene to downshift the Fermi energy and induce the Fermi instability that results in a spin polarized ground state. Within first-principles calculations, we observe antiferromagnetic spin alignment between adjacent ferromagnetic triangular domains where each Si atom is coupled with three neighboring P atoms with a ferromagnetic interaction. Such unique spin structure and resulting magnetic ground state are unprecedented in defect-free two-dimensional materials made of only p-block elements. This metal-free magnetism can be exploited for advanced spintronic and memory storage applications.