Cluster ion distributions of water in a molecular beam are investigated by
femtosecond ionization at 780 nm and reflectron time-of-flight mass spectro
metry. The electric field strength generated by the ultrashort laser pulses
is sufficient to efficiently ionize most of the molecules that are present
in the molecular beam. In this work ion signals of large water clusters co
ntaining up to 60 monomers are reported. Upon ionization rapid proton trans
fer is observed, leading to the formation of protonated water cluster ions.
Unprotonated clusters (H2O)(n)(+) (n>2) are not observed in the mass spect
ra. The configurational energy imparted to the protonated clusters induces
unimolecular dissociation on the ms time scale. These metastable reactions
are characterized by modeling the ion trajectories in the mass spectrometer
. The numerical procedure in conjunction with the integrated parent and dau
ghter intensities results in unimolecular dissociation rates as a function
of cluster size. Additional information about proton transfer reactions is
obtained by the investigation of deuterium substitutions. Even though these
substitutions correspond to large relative changes in the mass of the atom
as well as in the zero point energy, unprotonated (D2O)(n)(+) clusters of
significant abundance are not produced in supersonic expansions of deuterat
ed water. An additional result of this work is the observation of doubly ch
arged ions above a critical cluster size (n=37). (C) 1999 American Institut
e of Physics. [S0021-9606(99)01126-5].