Infrared spectroscopy of small protonated water clusters, H(+)(H2O)n (n = 2-5): isomers, argon tagging, and deuteration.
Infrared photodissociation spectroscopy is reported for mass-selected H(+)(H(2)O)(n) complexes and their deuterated analogues with and without argon "tagging." H(+)(H(2)O)(n)Ar(m) and D(+)(D(2)O)(n)Ar(m) complexes are studied in the O-H (O-D) stretching region for clusters in the small size range (n = 2-5). Upon infrared excitation, these clusters fragment by the loss of either argon atoms or one or more intact water molecules. Their excitation spectra show distinct bands in the region of the symmetric and asymmetric stretches of water and in the hydrogen bonding region. Experimental studies are complemented by computational work that explores the isomeric structures, their energetics and vibrational spectra. The addition of an argon atom is essential to obtain photodissociation for the n = 2-3 complexes, and specific inclusion of the argon in calculations is necessary to reproduce the measured spectra. For n = 3-5, spectra are obtained both with and without argon. The added argon atom allows selection of a subset of colder clusters and it increases the photodissociation yield. Although most of these clusters have more than one possible isomeric structure, the spectra measured correspond to a single isomer that is computed to be the most stable. Deuteration in these small cluster sizes leads to expected lowering of frequencies, but the spectra indicate the presence of the same single most-stable isomer for each cluster size.
Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556, USA.
G E
GE
Douberly
R S
RS
Walters
J
J
Cui
K D
KD
Jordan
M A
MA
Duncan
D001128:Argon / Q000737:chemistry*; D001665:Binding Sites; D019295:Computational Biology; D003903:Deuterium / Q000737:chemistry*; D006860:Hydrogen Bonding; D007536:Isomerism; D010777:Photochemistry; D011522:Protons; D013055:Spectrophotometry, Infrared; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
D011522:Protons; D014867:Water; D001128:Argon; D003903:Deuterium