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Heat Capacity Studies of Spin Crossover Systems

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Spin Crossover in Transition Metal Compounds III

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 235))

Abstract

As the spin crossover phenomena occurring in Oh symmetry involve a transfer of electrons between the eg and t2g orbitals, the metal-to-ligand bond distances change remarkably. This brings about a drastic change in the density of vibrational states, mainly the metal-ligand skeletal vibrational modes. Thus, the transition entropy due to the spin crossover involves a dominant contribution from the non-electronic vibrations in addition to the contribution from a change in the spin multiplicity. It is concluded that a coupling between the electronic states and the phonon system plays a fundamental role in the spin crossover occurring in the solid state. Heat capacity is a physical quantity containing contributions from all kinds of molecular degrees of freedom. Consequently calorimetry is a suitable experimental tool to help elucidate the mechanism involved in spin crossover phenomena.

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Abbreviations

phen:

1,10-Phenanthroline

LS:

Low spin

HS:

High spin

2-pic:

2-Aminomethylpyridine or 2-picolylamine

solv:

Solvated molecule

DTA:

Differential thermal analysis

acpa:

Hacpa=N-(1-acetyl-isopropylidene) (2-pyridylmethyl) amine

depe:

1,2-Bis(diethylphosphino)ethane

3EtO-salAPA:

3EtO-salAPAH is the Schiff base condensed from 1 mol of 3-ethoxysalicylaldehyde with 1 mol of N-aminopropylaziridine

S :

Molar entropy

H :

Molar enthalpy

G :

Molar Gibbs energy

R :

Gas constant

C p :

Molar heat-capacity under constant pressure

T :

Temperature

T 1/2 :

Spin transition temperature

γHS :

High-spin fraction

K :

Equilibrium constant

μ eff :

Effective magnetic moment

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Acknowledgements

I would like to thank my colleagues and students, in particular Prof. Philipp Gütlich and Prof. David N. Hendrickson, for their valued collaborations.

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  1. Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, 560-0043, Toyonaka, Osaka, Japan

    Michio Sorai

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  1. Michio Sorai
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Correspondence to Michio Sorai .

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Sorai, M. Heat Capacity Studies of Spin Crossover Systems. In: Spin Crossover in Transition Metal Compounds III. Topics in Current Chemistry, vol 235. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b95426

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  • DOI: https://doi.org/10.1007/b95426

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-40395-1

  • Online ISBN: 978-3-540-44984-3

  • eBook Packages: Springer Book Archive

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