Electronic Structure and d–d Spectrum of Metal–Organic Frameworks with Transition-Metal Ionsстатья
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Дата последнего поиска статьи во внешних источниках: 15 февраля 2024 г.
Аннотация:The electronic structure of metal-organic frameworks (MOFs) containing transition metal ions represents a significant and largely unresolved computational challenge due to limited solutions to the quantitative description of low-energy excitations in the open d-shells. These excitations underpin the magnetic and sensing properties of transition metal MOFs, including the observed remarkable spin-crossover phenomenon. We introduce the effective Hamiltonian of crystal field approach to study the d-d spectrum of MOFs containing transition metal ions; this is a hybrid QM/MM method based on the separation of crystal structure into d- and s,p-subsystems treated at different levels of theory. We test the method on model frameworks, carbodiimides and hydrocyanamides, and a series of M-MOF-74 (M = Fe, Co, and Ni) and compare the computational predictions to experimental data on magnetic properties and M \"ossbauer spectra.