First ionization potential, charge transfer

The photoelectron spectra of (Et3Si)2S and the silylalkyl sulphides (Et3Si(CH2)n)2S (n = 0-3) support a greater silyl donor influence for n = 0, 2 than for n = 1, 3, while the charge transfer spectra show a first ionization potential greatest for n = 036. 

Electrochemical dissolution is associated with current flow between anode and cathode. The dissolution of an atom from the anode surface involves (1) electrochemical reaction, (2) mass transport, and (3) charge transfer. First, the metal atoms on the anode surface are ionized (or oxidized) under the applied anodic potential ... 

The relatively low first ionization potential of 6 compared to fulvene can be rationalized by assuming a charge transfer due to the interaction of the symmetric le" orbital of the cyclopropane ring with the corresponding a orbital of the five-membered ring as discussed in case of spiro[4.2)heptatriene... 

For obvious reasons, the first ionization potential (I) and the electron affinity (A) of Ceo are of great importance to determining whether charge transfer between the guest molecule and the host Ceo cage is feasible in endohedral complexes. Thanks to several experimental studies [25,26,27], the value of I is known accurately and equals 7.61 0.02 eV. Despite its crudeness, Koopmans theorem [28] yields reasonable theoretical estimates for the ionization potential that are equal to 7.97 eV at the HF/4-31G level [3] and 8.03 eV at the HF/DZP level (see Section 5.1). For the electron affinity, the agreement is far less satisfactory, with the experimental value of 2.7 0.1 eV [29] compared to the theoretical A equal to 0.34 eV [3] at the HF/4-31G level. 

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