A semiempirical quantum chemical study of some local aspects of ionic conduction in poly(ethylene oxide)

Ion motion and rotational barriers

Vladimiro Mujica, Manuel Malaver, Fernando Ruette

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Several aspects of electronic potential energy curves for the ionic conduction process in poly(ethylene oxide) are modeled. A supermolecule is taken as a local model for a section of a polymer chain in the amorphous phase. Ion-polymer interaction, rotational barriers for the free and charged supermolecule, and the activation energy for intrachain ionic motion were calculated. For the latter, the oxygen-cation distance is considered as the reaction coordinate. The supermolecule assembly consists of five monomer units and a proton as probe ion. Strong coupling occurs between the motion of the ion and the flexional dynamics of the polymer that is manifest in the rearrangement that takes place in the nuclear framework of the chain as the position of the ion changes. The calculated activation energy was found in the range of the experimental values. All these results are consistent with the picture that ionic conduction in solid electrolytes such as poly(ethylene oxide) takes place mainly in the amorphous phase, because a considerable degree of flexibility on the polymer backbone is required to allow for the necessary bond rearrangements to promote cationic motion.

Original languageEnglish
Pages (from-to)89-94
Number of pages6
JournalJournal of Physical Chemistry A
Volume103
Issue number1
Publication statusPublished - Jan 7 1999

Fingerprint

Ionic conduction
ion motion
ethylene oxide
Polyethylene oxides
Polymers
Ions
conduction
polymers
Ionic conduction in solids
Activation energy
activation energy
ion probes
ions
Solid electrolytes
solid electrolytes
Potential energy
Cations
Protons
flexibility
monomers

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

A semiempirical quantum chemical study of some local aspects of ionic conduction in poly(ethylene oxide) : Ion motion and rotational barriers. / Mujica, Vladimiro; Malaver, Manuel; Ruette, Fernando.

In: Journal of Physical Chemistry A, Vol. 103, No. 1, 07.01.1999, p. 89-94.

Research output: Contribution to journalArticle

@article{d929b9eae7fe4c4aad261d6349effae6,
title = "A semiempirical quantum chemical study of some local aspects of ionic conduction in poly(ethylene oxide): Ion motion and rotational barriers",
abstract = "Several aspects of electronic potential energy curves for the ionic conduction process in poly(ethylene oxide) are modeled. A supermolecule is taken as a local model for a section of a polymer chain in the amorphous phase. Ion-polymer interaction, rotational barriers for the free and charged supermolecule, and the activation energy for intrachain ionic motion were calculated. For the latter, the oxygen-cation distance is considered as the reaction coordinate. The supermolecule assembly consists of five monomer units and a proton as probe ion. Strong coupling occurs between the motion of the ion and the flexional dynamics of the polymer that is manifest in the rearrangement that takes place in the nuclear framework of the chain as the position of the ion changes. The calculated activation energy was found in the range of the experimental values. All these results are consistent with the picture that ionic conduction in solid electrolytes such as poly(ethylene oxide) takes place mainly in the amorphous phase, because a considerable degree of flexibility on the polymer backbone is required to allow for the necessary bond rearrangements to promote cationic motion.",
author = "Vladimiro Mujica and Manuel Malaver and Fernando Ruette",
year = "1999",
month = "1",
day = "7",
language = "English",
volume = "103",
pages = "89--94",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "1",

}

TY - JOUR

T1 - A semiempirical quantum chemical study of some local aspects of ionic conduction in poly(ethylene oxide)

T2 - Ion motion and rotational barriers

AU - Mujica, Vladimiro

AU - Malaver, Manuel

AU - Ruette, Fernando

PY - 1999/1/7

Y1 - 1999/1/7

N2 - Several aspects of electronic potential energy curves for the ionic conduction process in poly(ethylene oxide) are modeled. A supermolecule is taken as a local model for a section of a polymer chain in the amorphous phase. Ion-polymer interaction, rotational barriers for the free and charged supermolecule, and the activation energy for intrachain ionic motion were calculated. For the latter, the oxygen-cation distance is considered as the reaction coordinate. The supermolecule assembly consists of five monomer units and a proton as probe ion. Strong coupling occurs between the motion of the ion and the flexional dynamics of the polymer that is manifest in the rearrangement that takes place in the nuclear framework of the chain as the position of the ion changes. The calculated activation energy was found in the range of the experimental values. All these results are consistent with the picture that ionic conduction in solid electrolytes such as poly(ethylene oxide) takes place mainly in the amorphous phase, because a considerable degree of flexibility on the polymer backbone is required to allow for the necessary bond rearrangements to promote cationic motion.

AB - Several aspects of electronic potential energy curves for the ionic conduction process in poly(ethylene oxide) are modeled. A supermolecule is taken as a local model for a section of a polymer chain in the amorphous phase. Ion-polymer interaction, rotational barriers for the free and charged supermolecule, and the activation energy for intrachain ionic motion were calculated. For the latter, the oxygen-cation distance is considered as the reaction coordinate. The supermolecule assembly consists of five monomer units and a proton as probe ion. Strong coupling occurs between the motion of the ion and the flexional dynamics of the polymer that is manifest in the rearrangement that takes place in the nuclear framework of the chain as the position of the ion changes. The calculated activation energy was found in the range of the experimental values. All these results are consistent with the picture that ionic conduction in solid electrolytes such as poly(ethylene oxide) takes place mainly in the amorphous phase, because a considerable degree of flexibility on the polymer backbone is required to allow for the necessary bond rearrangements to promote cationic motion.

UR - http://www.scopus.com/inward/record.url?scp=0001885398&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001885398&partnerID=8YFLogxK

M3 - Article

VL - 103

SP - 89

EP - 94

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 1

ER -