The reactions of Cl2O with the cluster ions X-(D2O)(n=0-4) (X = O, OD, O-2,
DO2, and O-3) were studied in a He buffer sas at temperatures within the r
ange 171-298 K and pressures of 0.27-0.51 Torr, using a flow-tube apparatus
. All ions were found to react with Cl2O at rates slower than predicted by
the collision rate and the charge center was transferred from X- to Cl- or
ClO-. The primary product ions Cl-(DOCl) and ClO-(DOCl) were observed to re
act further to produce the ions Cl3O- and Cl3O2-. The rate constants for th
e observed reactions are reported and the role that thermodynamics plays in
determining possible reaction channels is discussed. (C) 1999 Elsevier Sci
ence B.V.