Time-resolved studies of dynamics in molecular and cluster anions
- 1 January 1997
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Faraday Discussions
- Vol. 108, 101-113
- https://doi.org/10.1039/a705890j
Abstract
Femtosecond photoelectron spectroscopy (FPES) is used to study the time-resolved photodissociation dynamics of I2 -(CO2)n=4,16 clusters excited at 780 nm. The FPES experiment on I2 -(CO2)4 shows that the I- fragment formed by excitation to the A′2Π1/2,g repulsive state of I2 - initially pulls away from the cluster, but by 0.2 ps it is drawn back to complex with more of the solvent molecules. In the n=16 cluster, where caging of the I2 - is known to be complete, FPES probes the recombination dynamics of the I2 - in considerable detail. Specifically, vibrational relaxation on the I2 - X2Σu + state and the accompanying evaporation on CO2 molecules can be followed in real time. Vibrational relaxation is essentially complete by 10 ps, whereas solvent evaporation is not entirely complete by 200 ps. The spectra also show evidence for short-lived recombination on the I2 - A2Π3/2,g state. The results are compared to previous experimental results for I2 -(Ar)n clusters and recent simulations of cluster dynamics.Keywords
This publication has 0 references indexed in Scilit: