| Attributes | Values |
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| rdf:type
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| Description
| - 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).
- 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). (en)
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| Title
| - Excited state potential energy surfaces and their interactions in FeIV[double bond, length as m-dash]O active sites
- Excited state potential energy surfaces and their interactions in FeIV[double bond, length as m-dash]O active sites (en)
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| skos:prefLabel
| - Excited state potential energy surfaces and their interactions in FeIV[double bond, length as m-dash]O active sites
- Excited state potential energy surfaces and their interactions in FeIV[double bond, length as m-dash]O active sites (en)
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| skos:notation
| - RIV/61388955:_____/14:00434847!RIV15-AV0-61388955
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| http://linked.open...avai/riv/aktivita
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| http://linked.open...avai/riv/aktivity
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| http://linked.open...iv/cisloPeriodika
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| http://linked.open...vai/riv/dodaniDat
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| http://linked.open...aciTvurceVysledku
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| http://linked.open.../riv/druhVysledku
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| http://linked.open...iv/duvernostUdaju
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| http://linked.open...titaPredkladatele
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| http://linked.open...dnocenehoVysledku
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| http://linked.open...ai/riv/idVysledku
| - RIV/61388955:_____/14:00434847
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| http://linked.open...riv/jazykVysledku
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| http://linked.open.../riv/klicovaSlova
| - excited state potential energy; chemical analysis; Frontier molecular orbitals (en)
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| http://linked.open.../riv/klicoveSlovo
| |
| http://linked.open...odStatuVydavatele
| - GB - Spojené království Velké Británie a Severního Irska
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| http://linked.open...ontrolniKodProRIV
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| http://linked.open...i/riv/nazevZdroje
| |
| http://linked.open...in/vavai/riv/obor
| |
| http://linked.open...ichTvurcuVysledku
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| http://linked.open...cetTvurcuVysledku
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| http://linked.open...UplatneniVysledku
| |
| http://linked.open...v/svazekPeriodika
| |
| http://linked.open...iv/tvurceVysledku
| - Srnec, Martin
- Solomon, E. I.
- Wong, S. D.
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| http://linked.open...ain/vavai/riv/wos
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| issn
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| number of pages
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| http://bibframe.org/vocab/doi
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