The photodetachment dynamics of the iodide-aniline cluster, I- (C6 H5 N H2), were investigated using photoelectron-photofragment coincidence spectroscopy at several photon energies between 3.60 and 4.82 eV in concert with density functional theory calculations. Direct photodetachment from the solvated I- chromophore and a wavelength-independent autodetachment process were observed. Autodetachment is attributed to a charge-transfer-to-solvent reaction in which incipient continuum electrons photodetached from I- are temporarily captured by the nascent neutral iodine-aniline cluster configured in the anion geometry. Subsequent dissociation of the neutral cluster removes the stabilization, leading to autodetachment of the excess electron. The dependence of the dissociative photodetachment (DPD) and autodetachment dynamics on the final spin-orbit electronic state of the iodine fragment is characterized. The dissociation dynamics of the neutral fragments correlated with autodetached electrons were found to be identical to the DPD dynamics of the I atom product spin-orbit state closest to threshold at a given photon energy, lending support to the proposed sequential mechanism.
Dissociative photodetachment dynamics of the iodide-aniline cluster / MS. BOWEN; M. BECUCCI; RE. CONTINETTI. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - STAMPA. - 125:(2006), pp. 133309-1-133309-9. [10.1063/1.2210010]
Dissociative photodetachment dynamics of the iodide-aniline cluster
BECUCCI, MAURIZIO;
2006
Abstract
The photodetachment dynamics of the iodide-aniline cluster, I- (C6 H5 N H2), were investigated using photoelectron-photofragment coincidence spectroscopy at several photon energies between 3.60 and 4.82 eV in concert with density functional theory calculations. Direct photodetachment from the solvated I- chromophore and a wavelength-independent autodetachment process were observed. Autodetachment is attributed to a charge-transfer-to-solvent reaction in which incipient continuum electrons photodetached from I- are temporarily captured by the nascent neutral iodine-aniline cluster configured in the anion geometry. Subsequent dissociation of the neutral cluster removes the stabilization, leading to autodetachment of the excess electron. The dependence of the dissociative photodetachment (DPD) and autodetachment dynamics on the final spin-orbit electronic state of the iodine fragment is characterized. The dissociation dynamics of the neutral fragments correlated with autodetached electrons were found to be identical to the DPD dynamics of the I atom product spin-orbit state closest to threshold at a given photon energy, lending support to the proposed sequential mechanism.I documenti in FLORE sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.