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

Kreutzburg, Lars; Hübner, Christian G.; Paulsen, Hauke

doi:10.20944/preprints201701.0058.v1

2017

DOI: 10.20944/preprints201701.0058.v1

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

Lars Kreutzburg

Christian G. Hübner

Hauke Paulsen

Abstract: 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 simulation… Show more

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Cited by 2 publications

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Surface-Induced Electronic and Vibrational Level Shifting of [Fe(py)2bpym(NCS)2] on Al(100)

Zhang

2023

Materials

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It is essential that one understands how the surface degrees of freedom influence molecular spin switching to successfully integrate spin crossover (SCO) molecules into devices. This study uses density functional theory calculations to investigate how spin state energetics and molecular vibrations change in a Fe(II) SCO compound named [Fe(py)2bpym(NCS)2] when deposited on an Al(100) surface. The calculations consider an environment-dependent U to assess the local Coulomb correlation of 3d electrons. The results show that the adsorption configurations heavily affect the spin state splitting, which increases by 10–40 kJmol−1 on the surface, and this is detrimental to spin conversion. This effect is due to the surface binding energy variation across the spin transition. The preference for the low-spin state originates partly from the strong correlation effect. Furthermore, the surface environment constrains the vibrational entropy difference, which decreases by 8–17 Jmol−1K−1 (at 300 K) and leads to higher critical temperatures. These results suggest that the electronic energy splitting and vibrational level shifting are suitable features for characterizing the spin transition process on surfaces, and they can provide access to high-throughput screening of spin crossover devices.

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Surface-Induced Electronic and Vibrational Level Shifting of [Fe(py)2bpym(NCS)2] on Al(100)

Zhang

2023

Materials

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The Role of Vibrational Anharmonicity in the Computational Study of Thermal Spin Crossover

Sousa

Graaf

2019

Magnetochemistry

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Spin crossover in transition metal complexes can be studied in great detail with computational chemistry. Over the years, the understanding has grown that the relative stability of high-spin (HS) versus low-spin (LS) states is a subtle balance of many factors that all need to be taken into account for a reliable description. Among the different contributions, the zero-point energy (ZPE) and the entropy play key roles. These quantities are usually calculated assuming a harmonic oscillator model for the molecular vibrations. We investigated the impact of including anharmonic corrections on the ZPE and the entropy and indirectly on the critical temperature of spin crossover. As test systems, we used a set of ten Fe(II) complexes and one Fe(III) complex, covering different coordination modes (mono-, bi-, and tri-dentate ligands), decreasing coordination number upon spin crossover, coordination by second- and third-row atoms, and changes in the oxidation state. The results show that the anharmonicity has a measurable effect, but it is in general rather small, and tendencies are not easily recognized. As a conclusion, we put forward that for high precision results, one should be aware of the anharmonic effects, but as long as computational chemistry is still struggling with other larger factors like the influence of the environment and the accurate determination of the electronic energy difference between HS and LS, the anharmonicity of the vibrational modes is a minor concern.

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

Cited by 2 publications

References 38 publications

Surface-Induced Electronic and Vibrational Level Shifting of [Fe(py)2bpym(NCS)2] on Al(100)

Surface-Induced Electronic and Vibrational Level Shifting of [Fe(py)2bpym(NCS)2] on Al(100)

The Role of Vibrational Anharmonicity in the Computational Study of Thermal Spin Crossover

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