Electron detachment and fragmentation of laser-excited rotationally hotAl4−

Abstract

Absolute photoabsorption cross sections of negatively charged tetra-atomic aluminum clusters have been measured for photon energies between 1.8 and 2.7 eV. The experiment used the depletion technique in combination with an electrostatic ion-beam trap, in which ${{\mathrm{Al}}_{4}}^{\ensuremath{-}}$ ions produced in a sputter ion source were stored for 90 ms before being subjected to a short laser pulse. Moreover, the competition between one-atom fragmentation and electron emission of the laser-excited ${{\mathrm{Al}}_{4}}^{\ensuremath{-}}$ has been measured. These measurements show that fragmentation dominates electron emission at all photon energies below the electron attachment energy of $\ensuremath{\sim}2.2$ eV, even though the fragmentation energy is expected to be 10%--20% higher than the electron attachment energy. These findings, when taken together with the delayed-electron and fragmentation yields observed in a previous measurement [O. Aviv et al., Phys. Rev. A 83, 023201 (2011)], can be well explained within the statistical phase-space theory for unimolecular decays assuming the ${{\mathrm{Al}}_{4}}^{\ensuremath{-}}$ ions to be rotationally hot. The analysis permits the determination of the adiabatic electron detachment energy of ${{\mathrm{Al}}_{4}}^{\ensuremath{-}}$ to be ${E}_{\text{ad}}=(2.18\ifmmode\pm\else\textpm\fi{}0.02)$ eV and the one-atom fragmentation energy to be ${D}_{0}=(2.34\ifmmode\pm\else\textpm\fi{}0.05)$ eV. Moreover, two direct $s$-wave ionization channels are observed with threshold energies of $(2.18\ifmmode\pm\else\textpm\fi{}0.02)$ eV and $(2.45\ifmmode\pm\else\textpm\fi{}0.02)$ eV.