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Temperature‐modulated colloidal phase of plasmonic nanoparticles is a convenient playground for resettable soft‐actuators or colorimetric sensors. To render reversible clustering under temperature change, bulky ligands are required, especially if anisotropic morphologies are of interest. This study showcases thermoresponsive gold nanorods by employing small surface ligands, bis (p‐sulfonatophenyl) phenyl‐phosphine dihydrate dipotassium salt (BSPP) and native cationic surfactant. Temperature‐dependent analysis in real‐time allowed to describe the structural features (interparticle distance and cluster size) as well as thermal parameters, melting and freezing temperatures. These findings suggest that neither covalent Au−S bonds nor bulky ligands are required to obtain a robust thermoresponsive system based on anisotropic gold nanoparticles, paving the way to stimuli‐responsive nanoparticles with a wide range of sizes and geometries. [ABSTRACT FROM AUTHOR]

[Display omitted] A statistical thermodynamics variational criterion is propounded to study thermal hysteresis in reversible clustering of gold (Au) nanoparticles. Experimentally, a transient equilibrium mapping analysis is employed to characterize it thermodynamically, further measurements being performed at the nanostructural and electrochemical levels (UV-Vis-NIR spectra, SLS/SAXS, zeta potential). Theoretically, it is successfully interpreted as a thermodynamic cycle, prompting that nanoclusters has potential to produce useful work from heat and paving the way to nanoclustering heat engines. By taking into account the virial expansion of hysteretic pressure, an entropy measure is deduced for a dilute system with given virial coefficients. This allows us to figure out the role of relevant interparticle potential parameters (i.e. surface potential, nanoparticle size, Debye's length, Hamaker energy) in both isothermal and isochoric variations at the onset of hysteresis. Application to spherical Au nanoparticles in watery salt solution (NaCl) is developed when an ad-hoc (DLVO) pairwise potential governs the second virial coefficient at the nanoscale. In particular, the variational criterion predicts a pressure drop between heating and cooling paths which is likely at the base of some energy redistribution (e.g. ordering/restructuring of electric double layers). We found an integrating factor that is able to numerically predict the existence of a critical value for the initial salt concentration maximizing the hysteretic area, and the effect of nanoparticle size on the cycle extent. [ABSTRACT FROM AUTHOR]