TY - JOUR
T1 - Infrared photodissociation spectroscopy of H+(H 2O)6·Mm (M = Ne, Ar, Kr, Xe, H 2, N2, and CH4)
T2 - Messenger-dependent balance between H3O+ and H5O2+ core isomers
AU - Mizuse, Kenta
AU - Fujii, Asuka
PY - 2011/4/21
Y1 - 2011/4/21
N2 - Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H+(H2O)6·Mm (M = Ne, Ar, Kr, Xe, H2, N2, and CH4) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H+(H2O)6 moiety. The H+(H 2O)6, the protonated water hexamer, is the smallest system in which both the H3O+ (Eigen) and H5O 2+ (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H+(H 2O)6. The Xe-, CH4-, and N2-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N 2-, and CH4-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H2-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H +(H2O)6. These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.
AB - Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H+(H2O)6·Mm (M = Ne, Ar, Kr, Xe, H2, N2, and CH4) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H+(H2O)6 moiety. The H+(H 2O)6, the protonated water hexamer, is the smallest system in which both the H3O+ (Eigen) and H5O 2+ (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H+(H 2O)6. The Xe-, CH4-, and N2-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N 2-, and CH4-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H2-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H +(H2O)6. These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.
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U2 - 10.1039/c1cp20207c
DO - 10.1039/c1cp20207c
M3 - Article
C2 - 21399794
AN - SCOPUS:84855546044
VL - 13
SP - 7129
EP - 7135
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 15
ER -