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Can Hindered Intramolecular Vibrational Energy Redistribution Lead to Non‐Ergodic Behavior of Medium‐Sized Ion Pairs?
Author(s) -
Shaffer Christopher J.,
Révész Ágnes,
Schröder Detlef,
Severa Lukáš,
Teplý Filip,
Zins EmilieLaure,
Jašíková Lucie,
Roithová Jana
Publication year - 2012
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201203441
Subject(s) - intramolecular force , redistribution (election) , ion , trifluoromethanesulfonate , ergodic theory , chemical physics , ergodicity , chemistry , computer science , statistical physics , physics , stereochemistry , organic chemistry , mathematics , quantum mechanics , pure mathematics , politics , political science , law , catalysis
Communication breakdown : Ergodicity is the ability to predict the behavior of an ensemble from the behavior of its components. Infrared spectroscopy of mass‐selected ion pairs in the gas phase suggests that intramolecular vibrational energy redistribution (IVR) is hindered in some of these noncovalently bound species, particularly when triflate anion is involved. The hindered IVR leads to a non‐ergodic behavior on a timescale sufficient for the formation of new chemical bonds.