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Excited state potential energy surfaces and their interactions in FeIV[double bond, length as m-dash]O active sites
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SYSNO ASEP 0434847 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Excited state potential energy surfaces and their interactions in FeIV[double bond, length as m-dash]O active sites Tvůrce(i) Srnec, Martin (UFCH-W) RID, ORCID
Wong, S. D. (US)
Solomon, E. I. (US)Zdroj.dok. Dalton Transactions. - : Royal Society of Chemistry - ISSN 1477-9226
Roč. 43, č. 47 (2014), s. 17567-17577Poč.str. 11 s. Jazyk dok. eng - angličtina Země vyd. GB - Velká Británie Klíč. slova excited state potential energy ; chemical analysis ; Frontier molecular orbitals Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Institucionální podpora UFCH-W - RVO:61388955 UT WOS 000345065600002 EID SCOPUS 84911164305 DOI 10.1039/C4DT01366B Anotace The non-heme ferryl active sites are of significant interest for their application in biomedical and green catalysis. These sites have been shown to have an S = 1 or S = 2 ground spin state; the latter is functional in biology. Low-temperature magnetic circular dichroism (LT MCD) spectroscopy probes the nature of the excited states in these species including ligand-field (LF) states that are otherwise difficult to study by other spectroscopies. In particular, the temperature dependences of MCD features enable their unambiguous assignment and thus determination of the low-lying excited states in two prototypical S = 1 and S = 2 NHFeIV[double bond, length as m-dash]O complexes. Furthermore, some MCD bands exhibit vibronic structures that allow mapping of excited-state interactions and their effects on the potential energy surfaces (PESs). For the S = 2 species, there is also an unusual spectral feature in both near-infrared absorption and MCD spectra – Fano antiresonance (dip in Abs) and Fano resonance (sharp peak in MCD) that indicates the weak spin–orbit coupling of an S = 1 state with the S = 2 LF state. These experimental data are correlated with quantum-chemical calculations that are further extended to analyze the low-lying electronic states and the evolution of their multiconfigurational characters along the Fe–O PESs. These investigations show that the lowest-energy states develop oxyl FeIII character at distances that are relevant to the transition state (TS) for H-atom abstraction and define the frontier molecular orbitals that participate in the reactivity of S = 1 vs. S = 2 non-heme FeIV[double bond, length as m-dash]O active sites. The S = 1 species has only one available channel that requires the C–H bond of a substrate to approach perpendicular to the Fe–oxo bond (the π channel). Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2015
Počet záznamů: 1