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Issue 16, 2012
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Spin crossover transition of Fe(phen)2(NCS)2: periodic dispersion-corrected density-functional study

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Abstract

Periodic dispersion corrected DFT calculations have been performed to study the spin-crossover transition of Fe(phen)2(NCS)2 in the molecular and in the crystalline state. We show that London dispersion interactions play a crucial role in the cohesion of the crystals. Based on calculations of vibrational eigenstates of the isolated molecule and of the crystalline phase in both the low- and high-spin states, the transition entropies and enthalpies have been calculated. We demonstrate that, due to the stabilization of the low-spin state by intermolecular dispersion forces, the transition enthalpy at the transition temperature is larger for the crystalline phase in comparison with an isolated molecule. The effective coordination number of the nitrogen atoms of the ligands around the iron atom has been identified as the order parameter driving the quasi-reversible low-spin to high-spin transition in the crystal. Finally, using constrained geometry relaxations at fixed values of the coordination number, we computed the energy barrier of the LS to HS transition and found it to be in a reasonable agreement with the experimental value.

Graphical abstract: Spin crossover transition of Fe(phen)2(NCS)2: periodic dispersion-corrected density-functional study

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Publication details

The article was received on 12 Jan 2012, accepted on 22 Feb 2012 and first published on 23 Feb 2012


Article type: Paper
DOI: 10.1039/C2CP40111H
Citation: Phys. Chem. Chem. Phys., 2012,14, 5389-5396
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    Spin crossover transition of Fe(phen)2(NCS)2: periodic dispersion-corrected density-functional study

    T. Bučko, J. Hafner, S. Lebègue and J. G. Ángyán, Phys. Chem. Chem. Phys., 2012, 14, 5389
    DOI: 10.1039/C2CP40111H

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