Ultraviolet-visible photodissociation spectra of Vn+Xe (n=5–8) cluster complex cations

Abstract

Photodissociation spectra of vanadium cluster ion-xenon atom complexes Vn+Xe (n=5–8) have been measured between 290 and 670 nm. Spectra have been obtained by recording the depletion signal induced on the mass-selected cluster current intensity by the absorption of a photon. Due to the weak interaction between the ionic cluster and the rare-gas atom, photodissociation spectra are regarded as the absorption spectra of the vanadium cluster cations themselves. The absorption bands are broad, but several peaks can be resolved for the smallest sizes. The influence of the rare-gas atom on the electronic structure of the vanadium cluster cation is probed by performing the measurements on krypton instead of on xenon complexes. The features of the spectra do not change, but a blueshift of 0.12 eV is observed from krypton to xenon.

Structure Determination of Isolated Metal Clusters via Far-Infrared Spectroscopy

“…Monitoring the dissociation yield as a function of photon energy then gives the absorption spectrum. Although such techniques are used to measure UV, optical, and near infrared absorption spectra of vanadium [9,10] and other transition metal clusters [11][12][13][14], the lack of easily accessible intense and tuneable far infrared sources has prohibited so far the use of this method for the direct measurement of metal cluster vibrational spectra.…”

Dynamics of Clusters Initiated by Photon and Surface Impact

“…79,[83][84][85] A similar experiment has been performed for V N + Xe (N ) 5-8) complexes in the visible-near-ultraviolet range. 86 More recently, vibrational spectra of V N + Ar (N ) 6-23) have been reported in the 140-450-cm -1 region, 87 which were analyzed to determine the geometrical structures of V N + . 88 We discuss several outcomes of our studies of photodissociation dynamics by focusing in particular on electronic structures, chemical bonds, and magnetic properties of Ag 4 + , Mn N + , and Cr 3 + , in the following subsection.…”

“…Release of Ar atom was the only dissociation channel observed because the bond dissociation energy of V N + is higher than 3 eV; i.e., the spectra cannot be measured without the Ar atom. The spectra were analyzed by ab initio calculations; geometry optimization followed by calculations of transition energies and oscillator strengths. ,− A similar experiment has been performed for V N + Xe ( N = 5−8) complexes in the visible−near-ultraviolet range . More recently, vibrational spectra of V N + Ar ( N = 6−23) have been reported in the 140−450-cm -1 region, which were analyzed to determine the geometrical structures of V N + …”