How Accurately Can We Describe Spin Crossover?

Abstract The complicated physicochemical properties of metal complexes that exhibit thermal spin crossover make it difficult for routine electronic structure calculations to yield an accurate transition temperature prediction, T1/2. The difficulty lies in the intricate connection between the spin-crossover energy, which is a molecular spectroscopic property, and T1/2, a condensed-phase property. Here we show how to obtain spin-crossover energies systematically by reverse engineering of experimental T1/2 data. The protocol is based upon fitting the range separation parameter, ω, in the hybrid LC-ωPBE density functional to reproduce the experimental T1/2 values for a series of metal complexes. We provide insights into the sources of variations of at least ±15 kJ mol–1 found from common exchange and correlation functionals by comparing their performance against our reference data. By analysis of the sensitivity of transition temperatures to ±1% shifts in the range separation parameter, we determined a typical uncertainty of ±50 K for them, and a ±2 kJ mol–1 uncertainty in the extracted spin-crossover energies due to ±1% variations of T1/2. Lastly, we present results from the high-level, all-electron coupled cluster method for eight of the smaller molecules in the reference data set, and discuss the influence of the truncation of the excitation series upon the spin state energies.