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Title: Cation-ether complexes in the gas phase: Bond dissociation energies and equilibrium structures of Li{sup +} (1,2-dimethoxyethane){sub x}, x= 1 and 2, and Li{sup +}(12-crown-4)

Abstract

Bond dissociation energies, equilibrium structures, and harmonic vibrational frequencies are reported for Li{sup +}(DXE), where DXE= CH{sub 3}O(CH{sub 2}){sub 2}OCH{sub 3}, Li{sup +}(DXE){sub 2}, and Li{sup +}(12-crown-4). The bond dissociation energies are determined experimentally by analysis of the thresholds for collision-induced dissociation of the cation-ether complexes by xenon (measured using guided ion beam mass spectroscopy) and computationally by ab initio electronic structure calculations. For Li{sup +}(DXE){sub x}, x= 1 and 2, the primary and lowest energy dissociation channel observed experimentally is endothermic loss of one dimethoxyethane molecule. For Li{sup +}(12-crown-4), the primary dissociation channel is endothermic loss of the intact crown ether, although ligand fragmentation is also observed. The cross section thresholds are interpreted to yield 0 and 298 K bond energies after accounting for the effects of multiple ion-molecule collisions, internal energy of the complexes, and unimolecular decay rates. The calculated and experimentally-derived bond energies are in good agreement for Li{sup +}(DXE), are in reasonable agreement for Li{sup +}(12-crown-4), and differ by 32{+-}12 kJ/mol for Li{sup +}(DXE){sub 2}. The equilibrium structures are determined primarily by strong electrostatic and polarization interactions between Li{sup +} and the ligands. 65 refs., 7 figs., 5 tabs.

Authors:
; ;  [1]; ;  [2]
  1. Pacific Northwest National LAb., Richland, WA (United States)
  2. Univ. of Utah, Salt Lake City, UT (United States)
Publication Date:
OSTI Identifier:
420878
DOE Contract Number:  
AC06-76RL01830; FG06-89ER75522
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry; Journal Volume: 100; Journal Issue: 40; Other Information: PBD: 3 Oct 1996
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; 66 PHYSICS; 99 MATHEMATICS, COMPUTERS, INFORMATION SCIENCE, MANAGEMENT, LAW, MISCELLANEOUS; COMPLEXES; DISSOCIATION; DISSOCIATION ENERGY; MASS SPECTRA; ORGANOMETALLIC COMPOUNDS; CATIONS; ETHERS; CROWN ETHERS; GASES; CHEMICAL REACTION KINETICS; BOND LENGTHS; ION-MOLECULE COLLISIONS; CALCULATION METHODS; ELECTRONIC STRUCTURE

Citation Formats

Ray, D., Feller, D., Glendening, E.D., More, M.B., and Armentrout, P.B.. Cation-ether complexes in the gas phase: Bond dissociation energies and equilibrium structures of Li{sup +} (1,2-dimethoxyethane){sub x}, x= 1 and 2, and Li{sup +}(12-crown-4). United States: N. p., 1996. Web. doi:10.1021/jp961060n.
Ray, D., Feller, D., Glendening, E.D., More, M.B., & Armentrout, P.B.. Cation-ether complexes in the gas phase: Bond dissociation energies and equilibrium structures of Li{sup +} (1,2-dimethoxyethane){sub x}, x= 1 and 2, and Li{sup +}(12-crown-4). United States. doi:10.1021/jp961060n.
Ray, D., Feller, D., Glendening, E.D., More, M.B., and Armentrout, P.B.. Thu . "Cation-ether complexes in the gas phase: Bond dissociation energies and equilibrium structures of Li{sup +} (1,2-dimethoxyethane){sub x}, x= 1 and 2, and Li{sup +}(12-crown-4)". United States. doi:10.1021/jp961060n.
@article{osti_420878,
title = {Cation-ether complexes in the gas phase: Bond dissociation energies and equilibrium structures of Li{sup +} (1,2-dimethoxyethane){sub x}, x= 1 and 2, and Li{sup +}(12-crown-4)},
author = {Ray, D. and Feller, D. and Glendening, E.D. and More, M.B. and Armentrout, P.B.},
abstractNote = {Bond dissociation energies, equilibrium structures, and harmonic vibrational frequencies are reported for Li{sup +}(DXE), where DXE= CH{sub 3}O(CH{sub 2}){sub 2}OCH{sub 3}, Li{sup +}(DXE){sub 2}, and Li{sup +}(12-crown-4). The bond dissociation energies are determined experimentally by analysis of the thresholds for collision-induced dissociation of the cation-ether complexes by xenon (measured using guided ion beam mass spectroscopy) and computationally by ab initio electronic structure calculations. For Li{sup +}(DXE){sub x}, x= 1 and 2, the primary and lowest energy dissociation channel observed experimentally is endothermic loss of one dimethoxyethane molecule. For Li{sup +}(12-crown-4), the primary dissociation channel is endothermic loss of the intact crown ether, although ligand fragmentation is also observed. The cross section thresholds are interpreted to yield 0 and 298 K bond energies after accounting for the effects of multiple ion-molecule collisions, internal energy of the complexes, and unimolecular decay rates. The calculated and experimentally-derived bond energies are in good agreement for Li{sup +}(DXE), are in reasonable agreement for Li{sup +}(12-crown-4), and differ by 32{+-}12 kJ/mol for Li{sup +}(DXE){sub 2}. The equilibrium structures are determined primarily by strong electrostatic and polarization interactions between Li{sup +} and the ligands. 65 refs., 7 figs., 5 tabs.},
doi = {10.1021/jp961060n},
journal = {Journal of Physical Chemistry},
number = 40,
volume = 100,
place = {United States},
year = {Thu Oct 03 00:00:00 EDT 1996},
month = {Thu Oct 03 00:00:00 EDT 1996}
}