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Understanding (super-)exchange coupling between local spins is an important task in theoretical chemistry and solid-state physics. We show that a Green's-function approach introduced earlier (Liechtenstein et al., J. Phys. F 1984, 14, L125; Steenbock et al., J. Chem. Theory Comput. 2015, 11, 5651) can be used for analyzing exchange coupling pathways in an automated fashion rather than by visual inspection of molecular orbitals. We demonstrate the capabilities of this approach by comparing it to previously published pathway analyses for hydroxy-bridged dinuclear copper complexes and an oxo-bridged dinuclear manganese complex, and employ it for discriminating between through-space and through-bond pathways in a naphthalene-bridged bisnickelocene complex. © 2017 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

Molecules exhibiting a spin-crossover transition have been proposed for a number of applications such as molecular switches, spintronic tunable interfaces, and single molecule gates. Both the rational design of new spin-crossover systems and the improvement of the properties of the already existing ones require a theoretical understanding of the relative energy of the high (HS) and low spin state (LS) molecules in the solid-state. This has proved to be very challenging so far. Here, we shed some light on the importance of considering the symmetry and the geometry of the crystallographic cell to correctly evaluate the influence of the dipolar interactions on the relative energies of the molecular complex in both different spin states. Moreover, in the case of Fe(SCN)2(phen)2 dipolar interactions are found to play an important role for the stabilization of the LS complex. © 2016 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]