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Benchmarks for transition metal spin-state energetics: why and how to employ experimental reference data?
1Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krakow, Krakow, Poland. mradon@chemia.uj.edu.pl.
Physical Chemistry Chemical Physics : PCCP
|November 8, 2023
Summary
Accurate prediction of spin-state energy differences in transition metal complexes is crucial. This perspective reviews experimental data for benchmarking quantum chemistry methods, focusing on correcting environmental effects for reliable spin-state gap estimates.
Area of Science:
- Computational chemistry
- Inorganic chemistry
- Quantum chemistry
Background:
- Predicting spin-state energy differences in transition metal complexes is vital for computational inorganic chemistry.
- Accurate reference data for benchmarking quantum chemistry methods is challenging due to divergent results from high-level methods.
Purpose of the Study:
- To discuss two approaches for method benchmarking in spin-state energetics: theoretically computed versus experiment-derived reference data.
- To provide a comprehensive review of experimental spin-state energetics data for benchmark studies.
Main Methods:
- Focus on using experiment-derived reference data for benchmarking.
- Reviewing experimental data for spin-state energetics.
- Discussing back-correction of vibrational effects and environmental influences (solvents, crystalline environments).
Main Results:
- Experimental data can be interpreted to derive nearly chemically accurate estimates of electronic spin-state gaps.
- Environmental effects can be quantitatively modeled to improve benchmark accuracy.
- Understanding of spin-state phenomena in condensed phases is advanced.
Conclusions:
- Experiment-derived data, after correcting for environmental effects, offers a viable path to reliable benchmarks for spin-state energetics.
- This approach advances the theoretical modeling of spin crossover materials and open-shell reaction mechanisms.
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