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The electronic properties of interfaces can depend on their isotopicconstitution. One known case is that of cyclohexane physisorbed on Rh(111), inwhich isotope effects have been measured on the work function change anddesorption energies. These effects can only be captured by calculationsincluding nuclear quantum effects (NQE). In this paper, this interface isaddressed employing dispersion-inclusive density-functional theory coupled to aquasi-harmonic (QH) approximation for NQE, as well as to fully anharmonic abinitio path integral molecular dynamics (PIMD). The QH approximation is able tocapture that deuterated cyclohexane has a smaller adsorption energy and liesabout 0.01 A farther from the Rh(111) surface than its isotopologue, which canbe correlated to the isotope effect in the work function change. Aninvestigation of the validity of the QH approximation relying on PIMDsimulations, leads to the conclusion that although this interface is highlyimpacted by anharmonic quantum fluctuations in the molecular layer and atbonding sites, these anharmonic contributions play a minor role when analysingisotope effects at low temperatures. Nevertheless, anharmonic quantumfluctuations cause an increase in the distance between the molecular layer andRh(111), a consequent smaller overall work function change, and intricatechanges in orbital hybridization.

Quantum Nuclei at Weakly Bonded Interfaces: The Case of Cyclohexane on Rh(111)