Far-infrared spectra of inorganic nitrate and chloride glasses, liquids, and crystals: Complex ions or optical phonons?

Charles Angell, J. Wong, W. F. Edgeil

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

Polyethylene-sandwiched films of glassy and viscous liquid metal nitrate, nitrate-chloride, and chloride mixtures, sufficiently thin for their absorption spectra in the far ir to be determined in direct transmission studies, have been prepared. Comparisons of the spectra of these amorphous phases with spectra of the same thin-film samples after crystallization, have been made. Intense absorption bands arising from the vibrations of the quasilattices are observed in all instances, and in the case of the Cd(NO3) 2+TlNO3 glasses and liquids, the separate modes are almost as well defined as for the crystalline double salt TlNO3· Cd(NO3)2. The dependence of lattice vibration frequencies on cation charge and mass, and on cation mole fraction within a given binary system, have been studied. In the mixed systems frequency shifts to both high and lower values than those found in the individual components are observed. No reflections of the abrupt changes in thermodynamic and flow properties, which occur at the glass transition temperature, are found in the vibrational spectra. The nature of collective vibrational modes of motion in condensed phases and the relation of the common "complex-ion" interpretation of vibrational spectra in molten salts to the "quasilattice dynamics" view of the same spectra, are considered in some detail. Information on the internal modes of the NO3 - ion, and evidence for a distribution of NO3 - ion environments, in the glass, are also presented.

Original languageEnglish (US)
Pages (from-to)4519-4530
Number of pages12
JournalThe Journal of Chemical Physics
Volume51
Issue number10
StatePublished - 1969
Externally publishedYes

Fingerprint

inorganic nitrates
Liquid Crystals
Phonons
Nitrates
Chlorides
phonons
infrared spectra
chlorides
Vibrational spectra
Ions
Infrared radiation
Glass
vibrational spectra
Cations
nitrates
glass
Absorption spectra
liquids
Salts
crystals

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Far-infrared spectra of inorganic nitrate and chloride glasses, liquids, and crystals : Complex ions or optical phonons? / Angell, Charles; Wong, J.; Edgeil, W. F.

In: The Journal of Chemical Physics, Vol. 51, No. 10, 1969, p. 4519-4530.

Research output: Contribution to journalArticle

@article{bb6944525b1949e39522df227cbb8825,
title = "Far-infrared spectra of inorganic nitrate and chloride glasses, liquids, and crystals: Complex ions or optical phonons?",
abstract = "Polyethylene-sandwiched films of glassy and viscous liquid metal nitrate, nitrate-chloride, and chloride mixtures, sufficiently thin for their absorption spectra in the far ir to be determined in direct transmission studies, have been prepared. Comparisons of the spectra of these amorphous phases with spectra of the same thin-film samples after crystallization, have been made. Intense absorption bands arising from the vibrations of the quasilattices are observed in all instances, and in the case of the Cd(NO3) 2+TlNO3 glasses and liquids, the separate modes are almost as well defined as for the crystalline double salt TlNO3· Cd(NO3)2. The dependence of lattice vibration frequencies on cation charge and mass, and on cation mole fraction within a given binary system, have been studied. In the mixed systems frequency shifts to both high and lower values than those found in the individual components are observed. No reflections of the abrupt changes in thermodynamic and flow properties, which occur at the glass transition temperature, are found in the vibrational spectra. The nature of collective vibrational modes of motion in condensed phases and the relation of the common {"}complex-ion{"} interpretation of vibrational spectra in molten salts to the {"}quasilattice dynamics{"} view of the same spectra, are considered in some detail. Information on the internal modes of the NO3 - ion, and evidence for a distribution of NO3 - ion environments, in the glass, are also presented.",
author = "Charles Angell and J. Wong and Edgeil, {W. F.}",
year = "1969",
language = "English (US)",
volume = "51",
pages = "4519--4530",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "10",

}

TY - JOUR

T1 - Far-infrared spectra of inorganic nitrate and chloride glasses, liquids, and crystals

T2 - Complex ions or optical phonons?

AU - Angell, Charles

AU - Wong, J.

AU - Edgeil, W. F.

PY - 1969

Y1 - 1969

N2 - Polyethylene-sandwiched films of glassy and viscous liquid metal nitrate, nitrate-chloride, and chloride mixtures, sufficiently thin for their absorption spectra in the far ir to be determined in direct transmission studies, have been prepared. Comparisons of the spectra of these amorphous phases with spectra of the same thin-film samples after crystallization, have been made. Intense absorption bands arising from the vibrations of the quasilattices are observed in all instances, and in the case of the Cd(NO3) 2+TlNO3 glasses and liquids, the separate modes are almost as well defined as for the crystalline double salt TlNO3· Cd(NO3)2. The dependence of lattice vibration frequencies on cation charge and mass, and on cation mole fraction within a given binary system, have been studied. In the mixed systems frequency shifts to both high and lower values than those found in the individual components are observed. No reflections of the abrupt changes in thermodynamic and flow properties, which occur at the glass transition temperature, are found in the vibrational spectra. The nature of collective vibrational modes of motion in condensed phases and the relation of the common "complex-ion" interpretation of vibrational spectra in molten salts to the "quasilattice dynamics" view of the same spectra, are considered in some detail. Information on the internal modes of the NO3 - ion, and evidence for a distribution of NO3 - ion environments, in the glass, are also presented.

AB - Polyethylene-sandwiched films of glassy and viscous liquid metal nitrate, nitrate-chloride, and chloride mixtures, sufficiently thin for their absorption spectra in the far ir to be determined in direct transmission studies, have been prepared. Comparisons of the spectra of these amorphous phases with spectra of the same thin-film samples after crystallization, have been made. Intense absorption bands arising from the vibrations of the quasilattices are observed in all instances, and in the case of the Cd(NO3) 2+TlNO3 glasses and liquids, the separate modes are almost as well defined as for the crystalline double salt TlNO3· Cd(NO3)2. The dependence of lattice vibration frequencies on cation charge and mass, and on cation mole fraction within a given binary system, have been studied. In the mixed systems frequency shifts to both high and lower values than those found in the individual components are observed. No reflections of the abrupt changes in thermodynamic and flow properties, which occur at the glass transition temperature, are found in the vibrational spectra. The nature of collective vibrational modes of motion in condensed phases and the relation of the common "complex-ion" interpretation of vibrational spectra in molten salts to the "quasilattice dynamics" view of the same spectra, are considered in some detail. Information on the internal modes of the NO3 - ion, and evidence for a distribution of NO3 - ion environments, in the glass, are also presented.

UR - http://www.scopus.com/inward/record.url?scp=33750458486&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33750458486&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:33750458486

VL - 51

SP - 4519

EP - 4530

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 10

ER -