Surface-Induced Electronic and Vibrational Level Shifting of [Fe(py)(2)bpym(NCS)(2)] on Al(100)

It is essential that one understands how the surface degrees of freedom influence molecular spin switching to successfully integrate spin crossover (SCO) molecules into devices. This study uses density functional theory calculations to investigate how spin state energetics and molecular vibrations change in a Fe(II) SCO compound named [Fe(py)(2)bpym(NCS)(2)] when deposited on an Al(100) surface. The calculations consider an environment-dependent U to assess the local Coulomb correlation of [Formula: see text] electrons. The results show that the adsorption configurations heavily affect the spin state splitting, which increases by 10–40 [Formula: see text] on the surface, and this is detrimental to spin conversion. This effect is due to the surface binding energy variation across the spin transition. The preference for the low-spin state originates partly from the strong correlation effect. Furthermore, the surface environment constrains the vibrational entropy difference, which decreases by 8–17 [Formula: see text] (at 300 K) and leads to higher critical temperatures. These results suggest that the electronic energy splitting and vibrational level shifting are suitable features for characterizing the spin transition process on surfaces, and they can provide access to high-throughput screening of spin crossover devices.