title: Stalking Higher Energy Conformers on the Potential Energy Surface of Charged Species.
abstract: Combined theoretical DFT-MD and RRKM methodologies and experimental spectroscopic infrared predissociation (IRPD) strategies to map potential energy surfaces (PES) of complex ionic clusters are presented, providing lowest and high energy conformers, thresholds to isomerization, and cluster formation pathways. We believe this association not only represents a significant advance in the field of mapping minima and transition states on the PES but also directly measures dynamical pathways for the formation of structural conformers and isomers. Pathways are unraveled over picosecond (DFT-MD) and microsecond (RRKM) time scales while changing the amount of internal energy is experimentally achieved by changing the loss channel for the IRPD measurements, thus directly probing different kinetic and isomerization pathways. Demonstration is provided for Li(+)(H2O)3,4 ionic clusters. Nonstatistical formation of these ionic clusters by both direct and cascade processes, involving isomerization processes that can lead to trapping of high energy conformers along the paths due to evaporative cooling, has been unraveled.
authors.affiliation: LAMBE CNRS UMR8587, Université d'Evry val d'Essonne , Blvd F. Mitterrand, Bât Maupertuis, 91025 Evry, France.
authors.forename: Vincent
authors.initials: V
authors.lastname: Brites
authors.affiliation: LAMBE CNRS UMR8587, Université d'Evry val d'Essonne , Blvd F. Mitterrand, Bât Maupertuis, 91025 Evry, France.
authors.forename: Alvaro
authors.initials: A
authors.lastname: Cimas
authors.affiliation: LAMBE CNRS UMR8587, Université d'Evry val d'Essonne , Blvd F. Mitterrand, Bât Maupertuis, 91025 Evry, France.
authors.forename: Riccardo
authors.initials: R
authors.lastname: Spezia
authors.affiliation: Université Grenoble Alpes , DCM, 38000 Grenoble, France.|CNRS , DCM, 38000 Grenoble, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Sieffert
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign , Urbana, Illinois 61801, United States.
authors.forename: James M
authors.initials: JM
authors.lastname: Lisy
authors.affiliation: LAMBE CNRS UMR8587, Université d'Evry val d'Essonne , Blvd F. Mitterrand, Bât Maupertuis, 91025 Evry, France.|Institut Universitaire de France , 103 Blvd St Michel, 75005 Paris, France.
authors.forename: Marie-Pierre
authors.initials: MP
authors.lastname: Gaigeot
mesh_terms: D007700:Kinetics; D008094:Lithium / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D013499:Surface Properties; D013997:Time Factors; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D008094:Lithium