Total reorganization energy and its components in processes of one-electron oxidation of phosphorus compounds in acetonitrile

Research paper by V. V. Yanilkin, V. V. Zverev

Indexed on: 01 Apr '99Published on: 01 Apr '99Published in: Russian Chemical Bulletin


The ionization processes of phosphorus(III) and (IV) compounds oxidized in the potential range of 1.8–4.0 Vvs. Ag/0.01M AgNO3 in MeCN were studied by chronovoltammetry on a Pt ultramicroelectrode in acetonitrile and by photoelectron spectroscopy in the gas phase. A relationship between the half-wave potential (E1/2) and vertical ionization potential (IPv)E1/2=0.89IPv–6.27 is fulfilled in a wide potential range from−0.37 to 3.98 V. The total reorganization energy of the system (1.45–2.50 V) and the energy of reorganization of the solvate shell (0.9–1.9 eV) were estimated.