17. Theoretical Prediction of Spin-Crossover at the Molecular Level

  1. MALCOLM A. HALCROW
  1. Robert J. Deeth,
  2. Christopher M. Handley and
  3. Benjamin J. Houghton

Published Online: 18 JAN 2013

DOI: 10.1002/9781118519301.ch17

Spin-Crossover Materials: Properties and Applications

Spin-Crossover Materials: Properties and Applications

How to Cite

Deeth, R. J., Handley, C. M. and Houghton, B. J. (2013) Theoretical Prediction of Spin-Crossover at the Molecular Level, in Spin-Crossover Materials: Properties and Applications (ed M. A. HALCROW), John Wiley & Sons Ltd, Oxford, UK. doi: 10.1002/9781118519301.ch17

Editor Information

  1. School of Chemistry, University of Leeds, UK

Author Information

  1. Inorganic Computational Chemistry Group, Department of Chemistry, University of  Warwick, UK

Publication History

  1. Published Online: 18 JAN 2013
  2. Published Print: 15 FEB 2013

ISBN Information

Print ISBN: 9781119998679

Online ISBN: 9781118519301

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Keywords:

  • coordination complexes;
  • crystal field theory (CFT);
  • density functional theory (DFT);
  • ligand field molecular mechanics (LFMM);
  • quantum chemistry;
  • quantum mechanics;
  • semi-empirical MO theory;
  • spin crossover (SCO);
  • valence bond (VB)

Summary

This chapter explores the application of computational chemistry in its broadest sense to the calculation of spin state energetics of coordination complexes. Many applications of theory have not been directed to spin crossover (SCO) per se although clearly any method which can accurately predict the relative energies of different spin states could be applied to SCO. The chapter is arranged roughly along historical lines beginning with early crystal field theory (CFT) and valence bond (VB) approaches, which provided a qualitative description of spin states. It then discusses ab initio quantum mechanics and density functional theory (DFT). The chapter finally explores empirical methods, which use parameters to make computations significantly faster. These include semi-empirical MO theory and ligand field molecular mechanics. As for the future, the undoubted success of DFT and ligand field molecular mechanics (LFMM) to capture spin state energies of isolated complexes needs to be taken into solid state.