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On the Quantum Nature of an Excess Proton in Liquid Hydrogen Fluoride
Author(s) -
Raugei Simone,
Klein Michael L.
Publication year - 2004
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200400198
Subject(s) - delocalized electron , hydrogen fluoride , superacid , proton , chemistry , fluoride , chemical physics , hydrogen , molecule , quantum chemistry , ab initio , computational chemistry , molecular dynamics , density functional theory , ab initio quantum chemistry methods , hydrogen bond , inorganic chemistry , organic chemistry , supramolecular chemistry , physics , catalysis , quantum mechanics
Liquid hydrogen fluoride consists of chains of hydrogen‐bonded molecules. The nature of an excess proton in liquid HF, which is of interest not only for its own sake, but also in relation to superacid chemistry and to its behavior in water, has been studied using computer simulations. The methodology employed is the density‐functional‐theory‐based path‐integral Car–Parrinello ab initio molecular dynamics. The excess proton, which formally exists as a H 2 F + or a H 2 F 2 + defect in an HF chain, is found to strongly perturb the chain to which it is attached. Moreover, due to large zero‐point energy, the charge defect is largely delocalized over several HF molecules.