Dynamics of alkyl chains in monolayer protected metal clusters and their superlattices

Alkyl chains dynamics in monolayer protected metal cluster (MPC) systems of gold and silver have been studied by the quasielastic neutron scattering (QENS) technique. Isolated MPCs investigated are 6, 12 and 18 carbon n-alkyl chain thiolate protected 4 nm diameter gold clusters while the superlattices are their silver analogues. Evolution of dynamics with temperature is found to be very different in the isolated clusters and their superlattices. While continuous evolution of the dynamics of the monolayer was observed in isolated MPCs, it is abrupt in superlattice systems and occurs at a temperature consistent with the superlattice melting detected in calorimetry measurements. A model where the chain undergoes uniaxial rotational diffusion with additional body axis fluctuation was found to describe the data consistently. For the superlattice systems, the chains are found to be held by strong inter-chain interactions below the superlattice melting. The data from the planar silver thiolate systems show similar behavior like the superlattice systems, consistent with the calorimetric data.