Szeghalmi, Adriana V. 
; Erdmann, Marco ; Engel, Volker ; Schmitt, Michael ; Amthor, Stephan ; Kriegisch, Volker ; Nöll, Gilbert ; Stahl, Rainer ; Lambert, Christoph ; Leusser, Dirk ; Stalke, Dietmar ; Zabel, Manfred ; Popp, Jürgen
Alternative Links zum Volltext:DOIVerlag
| Dokumentenart: | Artikel |
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| Titel eines Journals oder einer Zeitschrift: | Journal of the American Chemical Society |
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| Verlag: | AMER CHEMICAL SOC |
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| Ort der Veröffentlichung: | WASHINGTON |
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| Band: | 126 |
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| Nummer des Zeitschriftenheftes oder des Kapitels: | 25 |
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| Seitenbereich: | S. 7834-7845 |
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| Datum: | 2004 |
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| Institutionen: | Chemie und Pharmazie > Zentrale Analytik |
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| Identifikationsnummer: | | Wert | Typ |
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| 10.1021/ja0395386 | DOI |
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| Stichwörter / Keywords: | MIXED-VALENCE SYSTEMS; CHARGE-TRANSFER TRANSITIONS; DENSITY-FUNCTIONAL THEORY; RAMAN INTENSITY ANALYSIS; NEAR-INFRARED REGION; CREUTZ-TAUBE ION; RESONANCE RAMAN; REORGANIZATION ENERGIES; METAL-COMPLEXES; ELECTROABSORPTION SPECTROSCOPY; |
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| Dewey-Dezimal-Klassifikation: | 500 Naturwissenschaften und Mathematik > 540 Chemie |
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| Status: | Veröffentlicht |
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| Begutachtet: | Ja, diese Version wurde begutachtet |
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| An der Universität Regensburg entstanden: | Ja |
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| Dokumenten-ID: | 71498 |
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Web of Science
Zusammenfassung
The electronic and molecular structure of N,N,N',N'-tetraphenylphenylenediamine radical cation 11 is in focus of this study. Resonance Raman experiments showed that at least eight vibrational modes are strongly coupled to the optical charge resonance band which is seen in the NIR. With the help of a DFT-based vibrational analysis, these eight modes were assigned to symmetric vibrations. The ...
Zusammenfassung
The electronic and molecular structure of N,N,N',N'-tetraphenylphenylenediamine radical cation 11 is in focus of this study. Resonance Raman experiments showed that at least eight vibrational modes are strongly coupled to the optical charge resonance band which is seen in the NIR. With the help of a DFT-based vibrational analysis, these eight modes were assigned to symmetric vibrations. The contribution of these symmetric modes to the total vibrational reorganization energy is dominant. These findings are in agreement with the conclusions from a simple two-state two-mode Marcus-Hush analysis which yields a tiny electron-transfer barrier. The excellent agreement of the X-ray crystal structure analysis and the DFT computed molecular structure of 11 on one hand as well as the solvent and solid-state IR spectra and the DFT-calculated IR active vibrations on the other hand prove 1(+) adopts a symmetrical delocalized Robin-Day class III structure both in the solid state and in solution.
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