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

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Abstract

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.

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

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Publication details

The article was received on 25 Sep 2018, accepted on 29 Oct 2018 and first published on 30 Oct 2018


Article type: Paper
DOI: 10.1039/C8CP06020G
Citation: Phys. Chem. Chem. Phys., 2018, Advance Article
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    Influence of argon and D2 tagging on the hydrogen bond network in Cs+(H2O)3; kinetic trapping below 40 K

    T. K. Esser, H. Knorke, F. Siro-Brigiano, D. R. Galimberti, K. R. Asmis, M. Gaigeot and J. M. Lisy, Phys. Chem. Chem. Phys., 2018, Advance Article , DOI: 10.1039/C8CP06020G

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