The temporary anion states of gas-phase diphenyldisulfide are characterised by means of electron transmission (ET) and dissociative electron attachment (DEA) spectroscopies. The measured energies of vertical electron attachment are compared with the virtual orbital energies of the neutral state molecule supplied by MP2 and B3LYP calculations with the 6-31G* basis set. The calculated energies, scaled with empirical equations, reproduce satisfactorily the attachment energies measured in the ET spectrum. The first anion state of diphenyldisulfide is stable, thus escaping detection in ETS. The vertical and adiabatic electron affinities, evaluated with B3LYP/6-31+G* calculations as the energy difference between the neutral and anion states, are predicted to be 0.37 and 1.38 eV, respectively. The anion current displayed in the DEA spectrum has a sharp and intense peak at zero energy, essentially due to the C6H5S- negative fragment. In agreement, according to the calculations, the localization properties of the first anion state are strongly S-S antibonding, and the energetic requirement for its dissociation along the S-S bond are fulfilled even at zero energy.
A. Modelli, D. Jones (2006). Temporary Anion States and Dissociative Electron Attachment in Diphenyl Disulfide. JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY, 110, 10219-10224 [10.1021/jp0628683].
Temporary Anion States and Dissociative Electron Attachment in Diphenyl Disulfide.
MODELLI, ALBERTO;
2006
Abstract
The temporary anion states of gas-phase diphenyldisulfide are characterised by means of electron transmission (ET) and dissociative electron attachment (DEA) spectroscopies. The measured energies of vertical electron attachment are compared with the virtual orbital energies of the neutral state molecule supplied by MP2 and B3LYP calculations with the 6-31G* basis set. The calculated energies, scaled with empirical equations, reproduce satisfactorily the attachment energies measured in the ET spectrum. The first anion state of diphenyldisulfide is stable, thus escaping detection in ETS. The vertical and adiabatic electron affinities, evaluated with B3LYP/6-31+G* calculations as the energy difference between the neutral and anion states, are predicted to be 0.37 and 1.38 eV, respectively. The anion current displayed in the DEA spectrum has a sharp and intense peak at zero energy, essentially due to the C6H5S- negative fragment. In agreement, according to the calculations, the localization properties of the first anion state are strongly S-S antibonding, and the energetic requirement for its dissociation along the S-S bond are fulfilled even at zero energy.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
