期刊
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
卷 14, 期 5, 页码 2446-2455出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.8b00057
关键词
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资金
- Flemish Science Foundation (FWO)
- KU Leuven Postdoctoral mandates [PDM/16/112]
- KU Leuven [C14/15/052]
- Hercules Foundation
- Flemish Government-department EWI
In previous work on the performance of multiconfigurational second-order perturbation theory (CASPT2) in describing spin state energetics in first-row transition metal systems [Pierloot et al. J. Chem. Theory Comput. 2017, 13, 537-553], we showed that standard CASPT2 works well for valence correlation but does not describe the metal semicore (3s3p) correlation effects accurately. This failure is partially responsible for the well-known bias toward high-spin states of CASPT2. In this paper, we expand our previous work and show that this bias could be partly removed with a combined CASPT2/CC approach: using high-quality CASPT2 with extensive correlation-consistent basis sets for valence correlation and low-cost CCSD(T) calculations with minimal basis sets for the metal semicore (3s3p) correlation effects. We demonstrate that this approach is efficient by studying the spin state energetics of a series of iron complexes modeling important intermediates in oxidative catalytic processes in chemistry and biochemistry. On the basis of a comparison with bare CCSD(T) results from this and previous work, the average error of the CASPT2/CC approach is estimated at around 2 kcal mol(-1) in favor of high spin states.
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