Fe L-Edge X-ray Absorption Spectra of Fe(II) Polypyridyl Spin Crossover Complexes from Time-Dependent Density Functional Theory

L-edge near-edge X-ray fine structure spectroscopy (NEXAFS) has become a powerful tool to study the electronic structure and dynamics of metallo-organic and biological compounds in solution. Here, we present a series of density functional theory calculations of Fe L-edge NEXAFS for spin crossover (SCO) complexes within the timedependent framework. Several key factors that control the L-edge excitations have been carefully examined using an Fe(II) polypyridyl complex [Fe(tren(py)3)]2+ (where tren(py)3 = tris(2-pyridylmethyliminoethyl)amine) as a model system. It is found that the electronic spectra of the low-spin (LS, singlet), intermediate-spin (IS, triplet), and high-spin (HS, quintet) states have distinct profiles. The relative energy positions, but not the spectral profiles, of different spin states are sensitive to the choice of the functionals. The inclusion of the vibronic coupling leads to almost no visible change in the resulting NEXAFS spectra because it is governed only by low-frequency modes of less than 500 cm−1. With the help of the molecular dynamics sampling in acetonitrile at 300 K, our calculations reveal that the thermal motion can lead to a noticeable broadening of the spectra. The main peak position is strongly associated with the length of the Fe−N bond.