期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 24, 期 26, 页码 6787-6797出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201705921
关键词
corroles; DET calculations; NEXAFS; silver; XAS
资金
- Austrian Science Fund (FWF) [D-A-CH i958]
- European Union via ERC Advanced Grant MolArt [247299]
- German Research Foundation (DFG) [KL 2294/3-1, FOR 1405, TRR 142]
- Munich-Centre for Advanced Photonics (MAP)
- Austrian Science Fund [FWF-P28167]
- Helmholtz-Zentrum Berlin
We demonstrate here that theory-assisted near edge X-ray absorption fine-structure (NEXAFS) spectroscopy enables the site-sensitive monitoring of on-surface chemical reactions, thus, providing information not accessible by other techniques. As a prototype example, we have used free-base 5,10,15-tris(pentafluorophenyl)corroles (3H-TpFPC) adsorbed on Ag(111) and present a detailed investigation of the angle-dependent NEXAFS of this molecular species as well as of their thermally induced derivatives. For this, we have recorded experimental C and N K-edge NEXAFS spectra and interpret them based on XAS cross-section calculations by using a continuous fraction approach and core-hole including multiprojector PAW pseudopotentials within DFT We have characterized the as-deposited low temperature (200 K) phase and unraveled the subsequent changes induced by dehydrogenation (at 330 K) and ring-closure reactions (at 430 K). By exemplarily obtaining profound insight into the on-surface chemistry of free-base corrolic species adsorbed on a noble metal this work highlights how angle dependent XAS combined with accurate theoretical modeling can serve for the investigation of on-surface reactions, whereby even highly similar molecular structures, such as tautomers and isomers, can be distinguished.
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