<p>Pressure-induced ordered fusion of ligand-capped supercrystals offers a convenient pathway for large-scale preparation of nanowires. In this study, atomistic molecular dynamics simulations are carried out to study the pressure-driven fusion of alkylthiol-passivated gold supercrystals and elucidate how nanocrystal parameters determine the assembly of well-ordered nanowire arrays. Consistent with previous experimental observations, our simulations reveal that uniaxial compression can trigger ordered fusion in gold supercrystals as the background hydrostatic pressure exceeds a critical value. The critical hydrostatic pressure is observed to markedly decrease with shorter ligand length and lower ligand packing density but show little dependence on the nanocrystal core size. We ascribe the underlying mechanisms to the shear modulus of gold supercrystals as well as its variations influenced by the alteration in ligand length, ligand packing density, and nanocrystal core size. Longer ligands or a higher ligand packing density reduce the shear modulus of the gold supercrystals and thereby requires higher hydrostatic pressure to enhance their shear modulus needed for nanowire array formation. However, the shear modulus remains almost unchanged with varying nanocrystal core size, so that the critical hydrostatic pressure is independent of the core size. These findings are expected to provide valuable insights for optimizing stress-driven nanofabrication methods.</p>