Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 113, Issue 37, Pages 10033-10039Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp900654j
Keywords
-
Funding
- Danish Natural Science Research Council [272-08-0041]
- The Danish Center for Scientific Computing
- Generalitat de Catalunya (Beatriu de Pinos Fellowship) [2006 BP-A 10041]
Ask authors/readers for more resources
Despite their importance in many chemical processes, the relative energies of spin states of transition metal complexes have so far been haunted by large computational errors. By the use of six functionals, B3LYP, BP86, TPSS, TPSSh, M06L, and M06L, this work studies nine complexes (seven with iron and two with cobalt) for which experimental enthalpies of spin crossover are available. It is shown that such enthalpies can be used as quantitative benchmarks of a functional's ability to balance electron correlation in both the involved states. TPSSh achieves an unprecedented mean absolute error of similar to 11 kJ/mol in spin transition energies, with the local functional M06L a distant second (25 kJ/mol). Other tested functionals give mean absolute errors of 40 kJ/mol or more. This work confirms earlier suggestions that 10% exact exchange is near-optimal for describing the electron correlation effects of first-row transition metal systems. Furthermore, it is shown that given an experimental structure of an iron complex, TPSSh can predict the electronic state corresponding to that experimental structure. We recommend this functional as current state-of-the-art for studying spin crossover and relative energies of close-lying electronic configurations in first-row transition metal systems.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available