Evaluation of Non‐covalent Binding Energies and Optoelectronic Properties of New CuBr2(C6H7N)2 Complex: DFT Approaches

Abstract

For the first time, the structural and optoelectronic properties of a new complex formulated as CuBr2(C6H7N)2 (1) [trans‐dibromidobis(3‐methylpyridine‐κN) copper(II)] were studied by density functional theory (DFT) calculations. They are performed using B3LYP through the Gaussian 09 program and also with full potential linearized augmented plane wave (FP‐LAPW) methods within the Generalized Gradient Approximation (GGA) and Hartree‐Fock (HF) theory by the Wien2k package. The neutral monomeric complex participates in a variety of non‐covalent interactions, including hydrogen bonding and π stacking to create a 2D coordinate plane. The binding energy value of the non‐covalent interactions responsible for the crystalline network formation of 1 were calculated using the method of dispersion corrected density functional theory (DFT‐D). In this method, the independent smallest fragment (monomer) and subsequently the related network, including seven monomers bearing all non‐covalent interactions were optimized. The results demonstrate that hydrogen bonds, especially non‐conventional C–H···Br interactions, govern the network formation along the a and c axes. It can be mentioned because of these directed interactions, increasing of charge transfer along x and z directions results in increasement of the absorption and refractive index along y and z directions, and vice versa. The results of band structure show indirectly and directly the nature of the bandgap within GGA and HF, respectively. The bandgap value of CuBr2(C6H7N)2 is comparable to those of binary semiconductor compounds. DOSs spectra reveal that 3d Cu, 4p Br, and 2p C states play important roles in the optical transitions of the electrons. The calculated electronic absorption of the UV/Vis spectrum shows six major electron‐transition bands derived from d → d (ligand field) n → n, n → π*, π → n, and σ → n MLCT and LMCT transitions. The calculated absorption spectrum of the titled complex through FP‐LAPW within GGA method shows good consistency with the B3LYP/def2‐TZVP/6‐311+G(d,p) method. Our calculated birefringence results show that 1 has capability of nonlinear optical, which can be used in the nonlinear optoelectronic devices.