Electron Affinities from Reduction Potentials and CURES-EC

2 Electron Affinities from Reduction Potentials and CURES-EC 

The electron affinities of the chlorobenzene isomers have been determined by scaling half-wave reduction potentials [22], With higher gas phase values higher values are obtained from reduction potentials. These are compared to the ECD and CURES-EC values in Table 11.9. The CURES-EC-calculated values for the above compounds support experimental quantities and suggest that the Ea of all halogenated benzenes can be calculated. The CURES-EC values are listed in Table 11.10. The Ea 

TABLE 11.10 Calculated Valence-State Electron Affinities (in eV) of Halobenzenes [this work] 

The electron affinities of several chlorinated biphenyls and chlorinated naphthalenes have been determined from half-wave reduction potentials [22]. The electron affinity of 1-C1 naphthalene measured in the ECD has been used to scale the values for the other chloronaphthalens. The solution energy differences were set to the same value, 2.05(5) eV, for compounds with the same number of chlorine atoms up to three chlorines. For four or more chlorines up to the fully chlorinated naphthalene the mddG is 1.95(5) eV. For the fully chlorinated compound the mddG is 1.85(5) eV. This gives for Ea a range of 0.3 to 1.57 eV or 0.2 eV/Cl atom from naphthalene to the fully chlorinated naphthalene. The CURES-EC calculations support these values. They are given in Table 11.11. 

---