“…The Au–thiol (Au–S) bond has long been discussed in experimental and theoretical studies owing to its importance in biosensing, , nanomedicine, drug delivery, molecular electronics, − molecular spintronics, − molecular recognition, , and noble metal nanoparticle catalysis. , Au–S interactions are used to stabilize different sizes of Au nanoclusters by passivating with thiolate ligands, giving a platform to study different aggregates of metal atoms with a myriad of functionalities . Self-assembled monolayers of thiol-anchored molecules on an Au surface have been the most characteristic systems studied for molecular scale devices for decades. , A number of surface analysis techniques like X-ray photoelectron spectroscopy (XPS), − near-edge X-ray absorption fine structure measurements (NEXAFS), scanning tunneling microscopy (STM), , auger electron spectroscopy (AES), temperature-programmed desorption (TPD), , high-resolution electron energy loss spectroscopy (EELS), and X-ray diffraction (XRD) have been used to study the intricate nature of Au–S bonding under different environmental conditions. , Comparing various experimental observations with theoretical predictions to arrive at a common consensus on the structure of the Au–S interface poses a challenge in itself, even though comparisons have been rigorously attempted.…”