Preprint Article Version 1 NOT YET PEER-REVIEWED

Cooperativity of Spin Crossover Complexes: Combining Periodic Density Functional Calculations and Monte Carlo Simulations

Institut für Physik, Universität zu Lübeck, Ratzeburger Allee 160, 23562 Lübeck, Germany
Version 1 : Received: 10 January 2017 / Approved: 11 January 2017 / Online: 11 January 2017 (09:17:46 CET)

How to cite: Kreutzburg, L.; Hübner, C.; Paulsen, H. Cooperativity of Spin Crossover Complexes: Combining Periodic Density Functional Calculations and Monte Carlo Simulations. Preprints 2017, 2017010058 (doi: 10.20944/preprints201701.0058.v1). Kreutzburg, L.; Hübner, C.; Paulsen, H. Cooperativity of Spin Crossover Complexes: Combining Periodic Density Functional Calculations and Monte Carlo Simulations. Preprints 2017, 2017010058 (doi: 10.20944/preprints201701.0058.v1).

Abstract

The total enthalpies of the 16 different spin configurations that can be realized in the unit cell of the archetype spin crossover complex [Fe(phen)2(NCS)2] (phen=1,2-phenanthroline) were calculated applying periodic density functional theory combined with the Hubbard model and the Grimme-D2 dispersion correction (DFT+U/D2). The obtained enthalpy differences between the individual spin configurations were used to determine spin couplings of an Ising-like model and subsequent Monte Carlo simulations for this model allowed to estimate the phenomenological interaction parameter Г of the Slichter-Drickamer model, which is commonly used to describe the cooperativity of the spin transition. The calculational procedure described here, which led to an estimate of about 3 kJ/mol1 for Г, in good agreement with experiment, may be used to predict from first principles how modifications of spin crossover complexes can change the character of the spin transition from gradual to abrupt and vice versa.

Subject Areas

spin crossover; density functional calculations; Hubbard model; solid state; Slichter-Drickamer model; Monte Carlo simulation; Ising model

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