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We present the first nearly atomistic molecular dynamics study ofnanorod-nanorod association in explicit solvent, showing that inter-rod forcescan be dominated by microscopic factors absent in common continuumdescriptions. Specifically, we find that alkane ligands on faceted CdS nanorodsin n-hexane undergo a temperature-dependent order-disorder transition akin tothat of self-assembled monolayers on macroscopic substrates. This collectiveligand alignment organizes nearby solvent molecules, strongly influencing thestatistics of rod-rod separation. The strong temperature-dependence of thismechanism could be exploited in the laboratory to manipulate and optimize theassembly of ordered structures.

Orientational Ordering of Passivating Ligands on CdS Nanorods in Solution Generates Strong Rod-Rod Interactions