Influence of argon and D<sub>2</sub> tagging on the hydrogen bond network in Cs<sup>+</sup>(H<sub>2</sub>O)<sub>3</sub>; kinetic trapping below 40 K - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2018

Influence of argon and D2 tagging on the hydrogen bond network in Cs+(H2O)3; kinetic trapping below 40 K

Résumé

The influence of enthalpic and entropic effects as well as of kinetic trapping processes on the structure of Ar/D2-tagged Cs+(H2O)3 clusters is studied by temperature-dependent infrared photodissociation spectroscopy combined with harmonic vibrational spectra calculations and anharmonic free energy profiles from finite temperature metadynamics molecular dynamics simulations. Each tag favors a different hydrogen bond network of water molecules, with Ar-tagging (vs. D2-tagging) of Cs+(H2O)3 leading to the lower energy conformation. The relative population of these conformers can be tuned over a temperature range of 12 to 21 K. The formation mechanisms of these tagged clusters can be deduced from the free energy profiles. This investigation demonstrates that a variety of factors, both thermodynamic and kinetic, play a role in the structure of flexible molecular species, even at cryogenic temperatures.
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Dates et versions

hal-02110442 , version 1 (25-04-2019)

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Tim K. Esser, Harald Knorke, Flavio Siro-Brigiano, Daria Ruth Galimberti, Knut R. Asmis, et al.. Influence of argon and D2 tagging on the hydrogen bond network in Cs+(H2O)3; kinetic trapping below 40 K. Physical Chemistry Chemical Physics, 2018, 20 (45), pp.28476-28486. ⟨10.1039/C8CP06020G⟩. ⟨hal-02110442⟩
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