Geometry optimization of isolated dithiolated molecules are first performed by applying B3LYP/def2-TZVP method in two distinct electronic states, i.e., closed shell singlet (CSS) and broken symmetry open shell singlet (OSS) state in ORCA 49 quantum chemical code. OSS states are treated using spin-unrestricted broken-symmetry Kohn-Sham (UKS-BS) method within the DFT framework, while spin-restricted (RKS) wavefunction is used for CSS states. Resolution of the identity (RI) approximation in conjunction with auxiliary basis set def2/J and chain of spheres (COSX) numerical integration is used to accelerate the calculations without losing its accuracy. Tight convergence limits and increased integration grids (grid5) are used throughout. The molecular junctions are then constructed by placing the optimized isolated dithiol molecules between two gold electrodes after removing the terminal hydrogen atoms of thiol groups and forming the S-Au bonds. The gold electrodes are approximated by nine-atomic gold clusters, arranged in hexagonal closed-packed fcc Au-111 surface. The Au-Au distance is set to 2.88 Å and Au-S distance is fixed to 2.40 Å, which is similar to our previous reported works. The electron transport calculations are performed using Non-Equilibrium Green's Func-tion combined with DFT (NEGF-DFT) as implemented in Artaios 53 using B3LYP exchange correlation functional in combination with LANL2DZ basis set. Accordingly, the model used in transmission calculations is divided into three regions: central (C) scattering region formed by the di-thiolated molecule, and the left (L) and right (R) electrode consisting of Au 9 clusters. The transmission function is computed in the spirit of Landauer-Büttiker 54 formalism using equation