Electronic coupling, electron-transfer reactions, nonadiabatic solvent effects

Figure 9.6 Pressure-effect on rates of some self-exchange electron-transfer reactions between metal ions comparison of observed volumes of activation with values calculated from classical Marcus theory for adiabatic reactions. The plot shows calculated and observed AP values (cm mol ) at mid-range of pressure (100 MPa, except 70 MPa for Fe(H20)g ) for adiabatic (filled symbols) and nonadiabatic (open circles) self-exchange in couples with rigid ligands. Solvents (o, ) water ( ) CD3CN (A) (CD3)2CO (V) CD3OD. Key (A,B) (C,D) Cu(dmp)2 (E-G) Ru(hfac)j (H) Fe(C5H5)2 (I-K) Mn(CN-t-Bu)g ...

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