Ästhetische Autonomie als Abnormität

Neymeyr, Barbara

doi:10.1515/9783110813593

Cited by 34 publications

(3 citation statements)

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“…The pure component spectra and the associated absorption and concentration profiles were extracted with an algorithm based on factor analysis. [25] In Figures 2, 4, and 6b,t he concentrations of the complexes were multiplied by the number of their iron atoms to facilitate identification of conversion processes. This is indicated with the entry "c (number of Fe per molecule)".…”

Section: Methodsmentioning

confidence: 99%

Mechanistic Study of Photocatalytic Hydrogen Generation with Simple Iron Carbonyls as Water Reduction Catalysts

et al. 2015

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This study provides new insights into light‐driven hydrogen generation using an iridium photosensitizer (IrPS) and simple iron carbonyls as water reduction catalysts (WRCs). Stopped‐flow rapid‐scan FTIR and operando continuous‐flow FTIR spectroscopy as well as time‐dependent density functional theory (TD‐DFT) has been applied to study the reaction. The conversion of the WRC precursor [Fe3(CO)12] into the radicals [Fe3(CO)11].− and [Fe2(CO)8].− as well as [Fe(CO)5] in the absence of light in a solvent mixture of tetrahydrofuran, triethylamine, and water has been studied quantitatively. During light‐induced hydrogen production in the presence of the IrPS, the trimeric [HFe3(CO)11]− and the monomeric [HFe(CO)4]− anion could be identified as major WRC species. The equilibrium between both species can be shifted completely towards [HFe(CO)4]− by increasing the water content of the solvent mixture. Application of other iron(0) carbonyl compounds as WRC precursors also results in the exclusive formation of [HFe(CO)4]−. Kinetic experiments show that the stability of the system is primarily influenced by the applied amount of WRC precursor, whereas the reaction rate is mainly determined by the concentration of the IrPS. At least two loss channels could be identified: light‐induced CO dissociation from the WRC and decomposition of the IrPS at high IrPS/WRC ratios, accompanied by a ligand transfer from the iridium towards the iron center of the WRC. To reveal the nature of the catalytically active complex, binding energies and charge‐transfer probabilities of all coordination geometries of various IrPS⋅⋅⋅WRC complexes have been calculated. These computations indicate an increased probability of charge transfer for dimeric and trimeric iron carbonyl species.

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Section: Methodsmentioning

confidence: 99%

Mechanistic Study of Photocatalytic Hydrogen Generation with Simple Iron Carbonyls as Water Reduction Catalysts

et al. 2015

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“…For three components, three scores are estimated, but scaling the second and third score after division by the first one leads to two variables ( t 12 and t 13 ) allowing for a simplified presentation in two dimensions 7 . This produces a series of AFSs in abstract space, as shown in Figure 5, drawn by computing the convex hulls of the corresponding data points, provided the AFSs comply with the convexity property (it can be demonstrated that the SW‐N‐BANDS projections in the principal component space lie in the border of the AFSs) 27 . It is apparent that the AFSs reduce in size on increasing the constraints to the model, and that they increase when going from noiseless to noisy data.…”

Section: Resultsmentioning

confidence: 99%

“…7 This produces a series of AFSs in abstract space, as shown in Figure 5, drawn by computing the convex hulls of the corresponding data points, provided the AFSs comply with the convexity property (it can be demonstrated that the SW-N-BANDS projections in the principal component space lie in the border of the AFSs). 27 It is apparent that the AFSs reduce in size on increasing the constraints to the model, and that they increase when going from noiseless to noisy data.…”

Section: Simulationsmentioning

confidence: 99%

Two new methods for the estimation and interpretation of the range of feasible profiles in multivariate curve resolution and their implications to analytical chemistry

Olivieri

2024

Journal of Chemometrics

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Two new models have been recently introduced for studying the remaining rotational ambiguity in the bilinear decomposition of matrix data. One of the models is N‐BANDS, which yields two extreme profiles per sample component, corresponding to maximum or minimum signal contribution function or relative component area under its concentration profile. It is highly useful for computing the relative root mean square error due to rotational ambiguity in estimated analyte concentrations (RMSERA), which numerically quantifies the impact of the phenomenon in terms of prediction uncertainty. Since N‐BANDS successfully consider the presence of instrumental noise in the data, it is extremely useful for the analysis of real data sets. The other model is SW‐N‐BANDS, which is similar to N‐BANDS, but is applied in a sensor wise manner, that is, computing the maximum and minimum intensity value at each sensor. It provides the boundaries of the full set of feasible profiles, and helps to better understand the behavior of a given component under the application of several constraints. Both models are described in light of both simulations and experimental data, illustrating their main characteristics of importance to analytical chemistry studies.

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The Artist as Subject of Pure Cognition

Koßler¹

2011

A Companion to Schopenhauer

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Ästhetische Autonomie als Abnormität

Cited by 34 publications

References 0 publications

Mechanistic Study of Photocatalytic Hydrogen Generation with Simple Iron Carbonyls as Water Reduction Catalysts

Mechanistic Study of Photocatalytic Hydrogen Generation with Simple Iron Carbonyls as Water Reduction Catalysts

Two new methods for the estimation and interpretation of the range of feasible profiles in multivariate curve resolution and their implications to analytical chemistry

The Artist as Subject of Pure Cognition

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