Theoretical inspection of the spin-crossover [Fe(tzpy)₂(NCS)₂] complex on Au(100) surface

We explore the deposition of the spin-crossover [Fe(tzpy)₂(NCS)₂] complex on the Au(100) surface by means of density functional theory (DFT) based calculations. Two different routes have been employed: low-cost finite cluster-based calculations, where both the Fe complex and the surface are maintained fixed while the molecule approaches the surface; and periodic DFT plane-wave calculations, where the surface is represented by a four-layer slab and both the molecule and surface are relaxed. Our results show that the bridge adsorption site is preferred over the on-top and fourfold hollow ones for both spin states, although they are energetically close. The LS molecule is stabilized by the surface, and the HS-LS energy difference is enhanced by about 15%-25% once deposited. The different Fe ligand field for LS and HS molecules manifests on the composition and energy of the low-lying bands. Our simulated STM images indicate that it is possible to distinguish the spin state of the deposited molecules by tuning the bias voltage of the STM tip. Finally, it should be noted that the use of a reduced size cluster to simulate the Au(100) surface proves to be a low-cost and reliable strategy, providing results in good agreement with those resulting from state-of-the-art periodic calculations for this system.