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We study theoretically and experimentally the infrared (IR) spectrum of anadamantane monolayer on a Au(111) surface. Using a new STM-based IRspectroscopy technique (IRSTM) we are able to measure both the nanoscalestructure of an adamantane monolayer on Au(111) as well as its infraredspectrum, while DFT-based ab initio calculations allow us to interpret themicroscopic vibrational dynamics revealed by our measurements. We find that theIR spectrum of an adamantane monolayer on Au(111) is substantially modifiedwith respect to the gas-phase IR spectrum. The first modification is caused bythe adamantane--adamantane interaction due to monolayer packing and it reducesthe IR intensity of the 2912 cm$^{-1}$ peak (gas phase) by a factor of 3.5. Thesecond modification originates from the adamantane--gold interaction and itincreases the IR intensity of the 2938 cm$^{-1}$ peak (gas phase) by a factorof 2.6, and reduces its frequency by 276 cm$^{-1}$. We expect that thetechniques described here can be used for an independent estimate of substrateeffects and intermolecular interactions in other diamondoid molecules, and forother metallic substrates.

Intermolecular interactions and substrate effects for an adamantane monolayer on the Au(111) surface