Effect of pressure-induced freezing on the energy of the intervalence transfer electronic absorption band of binuclear mixed-valence complexes |
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| Affiliation: | 1. Jiangxi University of Science and Technology, Ganzhou, Jiangxi 341000, China;2. Institute of Geographic Sciences and Natural Resources Research, Chinese Academy of Sciences, Beijing 100101, China;3. Center for Environmental Risk and Damage Assessment, Chinese Academy for Environmental Planning, Beijing 100012, China;1. Department of Mathematics, Massachusetts Institute of Technology, Cambridge, MA 02139, USA;2. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA;1. Department of Mathematics, Massachusetts Institute of Technology, Cambridge, MA 02139, USA;2. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA;1. Faculty of Physics M.V. Lomonosov Moscow State University, 1-2 Leninskiye Gory, GSP-1, Moscow 119991, Russia;2. A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky Prospect, Moscow 119991, Russia;3. Faculty of Chemistry, M.V. Lomonosov Moscow State University, 1-3 Leninskiye Gory, GSP-1, Moscow, 119991, Russia;4. A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova St., Moscow, 119991, Russia |
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| Abstract: | The Marcus continuum model for the solvent reorientation contribution to the energetics of outer-sphere electron transfer has often been used to analyze the energy of the intervalence transfer (IT) electronic absorption band for a binuclear mixed-valence transition-metal complex. Eop, the energy required to transfer an electron optically in a mixed-valence complex, was measured as a function of pressure for two binuclear mixed-valence complexes in different solvents which freeze at 25°C under pressures < 10 kbar. Essentially no shifts of the IT bands were observed, indicating the inadequacy of the dielectric continuum model for such complexes. |
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