Photodissociation of (SO2)m(H2O)n clusters employing femtosecond pump-probe spectroscopy.
A femtosecond pump-probe technique was employed to study the photodissociation dynamics of (SO2)m(H2O)n clusters in real time for clusters, where m=1, 2 and n as large as 11. The pump (excitation) step occurs through a multiphoton process which populates the dissociative E state as well as a lower-lying bound state of the sulfur dioxide (SO2) chromophore. Dissociation of the SO2 monomer occurs through the E state and the decay is fit to a lifetime of 230 fs. The present study is in agreement with our previous investigations of homogeneous (SO2)m clusters that have shown that cluster formation inhibits the dissociation process owing to a steric effect induced by the cluster environment [K. L. Knappenberger, Jr. and A. W. Castleman, Jr., J. Chem. Phys. 121, 3540 (2004)]. The E state lifetime increases sequentially as a function of cluster size to as much as 668 fs when 11 water molecules solvate the chromophore. We have employed a method to compare the ratio of amplitude coefficients, which reflect a respective component of the mathematical fit, to determine the nature of the wave packet evolution in binary clusters. An increase of this ratio by as much as 440% was observed for large cluster sizes. A preferential ion state charge transfer, rather than dissociation, was observed in binary clusters. The significance of cluster size on evaporation processes has been investigated.
Knappenberger
K L
KL
Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802, USA.
Castleman
A W
AW