Abstract
Spin-crossover (SCO) materials have for more than 30 years stood out for their vast application potential in memory, sensing and display devices. To reach magnetic multistability conditions, the high-spin (HS) and low-spin (LS) states have to be carefully balanced by ligand field stabilization and spin-pairing energies. Both effects could be effectively modelled by electronic structure theory, if the description would be accurate enough to describe these concurrent influences to within a few kJ/mol. Such a milestone would allow for the in silico-driven development of SCO complexes. However, so far, the ab initio simulation of such systems has been dominated by general gradient approximation density functional calculations. The latter can only provide the right answer for the wrong reasons, given that the LS states are grossly over-stabilized. In this contribution, we explore different venues for the parameterization of hybrid functionals. A fitting set is provided on the basis of explicitly correlated coupled cluster calculations, with single- and multi-dimensional fitting approaches being tested to selected classes of hybrid functionals (hybrid, range-separated, and local hybrid). Promising agreement to benchmark data is found for a rescaled PBE0 hybrid functional and a local version thereof, with a discussion of different atomic exchange factors.
Highlights
Spin-crossover (SCO) complexes are molecules which exhibit spin transitions under external stimuli such as temperature and pressure, commonly based on d4 to d7 transition metals
The ab initio simulation of such systems has been dominated by general gradient approximation density functional calculations
A fitting set is provided on the basis of explicitly correlated coupled cluster calculations, with single- and multi-dimensional fitting approaches being tested to selected classes of hybrid functionals
Summary
Spin-crossover (SCO) complexes are molecules which exhibit spin transitions under external stimuli such as temperature and pressure, commonly based on d4 to d7 transition metals. Some of the most notable examples for SCO materials are based on Fe(II) [1], whereby the transition occurs between the S = 0 and the S = 2 states. These complexes have a wide potential application as molecular switches for use in display, memory and sensing devices [2,3,4,5]. Supramolecular complexes combining several metal centers have been developed over the last few years [6,7,8] The latter have gathered some interest given their unique SCO properties, allowing for hysteretic and multistep transitions
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