The local structure of triphenyl phosphite studied using spallation neutron and high-energy X-ray diffraction

Qiang Mei, Prasanna Ghalsasi, Chris J. Benmore, Jeffery Yarger

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Spallation neutron and high-energy X-ray diffraction experiments have been performed to investigate the local structural changes in triphenyl phosphite (TPP) in the crystalline, glacial, glassy, and supercooled liquid phases. The hydrogen/deuterium first-order difference method shows a large increase in intensity due to additional hydrogen correlations in the crystalline spectra compared to the glass and supercooled liquid at ∼3.0 and 3.4 Å. These features are shown to be largely due to inter-phenyl ring H-C/H interactions, which are probably associated in part with the formation of weak intermolecular hydrogen bonds. The high-energy X-ray diffraction data show a decrease in correlations at 3.12 Å which is attributed to changes in C-O/P intramolecular interactions between the glacial and crystalline forms. The structural evolution of the glacial state was also measured over time using total neutron diffraction. The largest structural differences between the early glacial and crystalline states are observed at 3.0 and 4.5 Å. Moreover, as the transformation progresses, the glacial spectra cannot be adequately described as a simple mixture of supercooled liquid and crystalline components. These results suggest that changes in molecular conformation and nearest-neighbor interactions are responsible for the existence of the glacial state.

Original languageEnglish (US)
Pages (from-to)20076-20082
Number of pages7
JournalJournal of Physical Chemistry B
Volume108
Issue number52
DOIs
StatePublished - Dec 30 2004
Externally publishedYes

Fingerprint

spallation
Neutrons
Crystalline materials
neutrons
X ray diffraction
diffraction
x rays
interactions
hydrogen
liquids
Hydrogen
Liquids
neutron diffraction
energy
deuterium
liquid phases
hydrogen bonds
Deuterium
Neutron diffraction
glass

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

The local structure of triphenyl phosphite studied using spallation neutron and high-energy X-ray diffraction. / Mei, Qiang; Ghalsasi, Prasanna; Benmore, Chris J.; Yarger, Jeffery.

In: Journal of Physical Chemistry B, Vol. 108, No. 52, 30.12.2004, p. 20076-20082.

Research output: Contribution to journalArticle

@article{d47bf063776a4c9ab683b2de866b3fa5,
title = "The local structure of triphenyl phosphite studied using spallation neutron and high-energy X-ray diffraction",
abstract = "Spallation neutron and high-energy X-ray diffraction experiments have been performed to investigate the local structural changes in triphenyl phosphite (TPP) in the crystalline, glacial, glassy, and supercooled liquid phases. The hydrogen/deuterium first-order difference method shows a large increase in intensity due to additional hydrogen correlations in the crystalline spectra compared to the glass and supercooled liquid at ∼3.0 and 3.4 {\AA}. These features are shown to be largely due to inter-phenyl ring H-C/H interactions, which are probably associated in part with the formation of weak intermolecular hydrogen bonds. The high-energy X-ray diffraction data show a decrease in correlations at 3.12 {\AA} which is attributed to changes in C-O/P intramolecular interactions between the glacial and crystalline forms. The structural evolution of the glacial state was also measured over time using total neutron diffraction. The largest structural differences between the early glacial and crystalline states are observed at 3.0 and 4.5 {\AA}. Moreover, as the transformation progresses, the glacial spectra cannot be adequately described as a simple mixture of supercooled liquid and crystalline components. These results suggest that changes in molecular conformation and nearest-neighbor interactions are responsible for the existence of the glacial state.",
author = "Qiang Mei and Prasanna Ghalsasi and Benmore, {Chris J.} and Jeffery Yarger",
year = "2004",
month = "12",
day = "30",
doi = "10.1021/jp046762o",
language = "English (US)",
volume = "108",
pages = "20076--20082",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "52",

}

TY - JOUR

T1 - The local structure of triphenyl phosphite studied using spallation neutron and high-energy X-ray diffraction

AU - Mei, Qiang

AU - Ghalsasi, Prasanna

AU - Benmore, Chris J.

AU - Yarger, Jeffery

PY - 2004/12/30

Y1 - 2004/12/30

N2 - Spallation neutron and high-energy X-ray diffraction experiments have been performed to investigate the local structural changes in triphenyl phosphite (TPP) in the crystalline, glacial, glassy, and supercooled liquid phases. The hydrogen/deuterium first-order difference method shows a large increase in intensity due to additional hydrogen correlations in the crystalline spectra compared to the glass and supercooled liquid at ∼3.0 and 3.4 Å. These features are shown to be largely due to inter-phenyl ring H-C/H interactions, which are probably associated in part with the formation of weak intermolecular hydrogen bonds. The high-energy X-ray diffraction data show a decrease in correlations at 3.12 Å which is attributed to changes in C-O/P intramolecular interactions between the glacial and crystalline forms. The structural evolution of the glacial state was also measured over time using total neutron diffraction. The largest structural differences between the early glacial and crystalline states are observed at 3.0 and 4.5 Å. Moreover, as the transformation progresses, the glacial spectra cannot be adequately described as a simple mixture of supercooled liquid and crystalline components. These results suggest that changes in molecular conformation and nearest-neighbor interactions are responsible for the existence of the glacial state.

AB - Spallation neutron and high-energy X-ray diffraction experiments have been performed to investigate the local structural changes in triphenyl phosphite (TPP) in the crystalline, glacial, glassy, and supercooled liquid phases. The hydrogen/deuterium first-order difference method shows a large increase in intensity due to additional hydrogen correlations in the crystalline spectra compared to the glass and supercooled liquid at ∼3.0 and 3.4 Å. These features are shown to be largely due to inter-phenyl ring H-C/H interactions, which are probably associated in part with the formation of weak intermolecular hydrogen bonds. The high-energy X-ray diffraction data show a decrease in correlations at 3.12 Å which is attributed to changes in C-O/P intramolecular interactions between the glacial and crystalline forms. The structural evolution of the glacial state was also measured over time using total neutron diffraction. The largest structural differences between the early glacial and crystalline states are observed at 3.0 and 4.5 Å. Moreover, as the transformation progresses, the glacial spectra cannot be adequately described as a simple mixture of supercooled liquid and crystalline components. These results suggest that changes in molecular conformation and nearest-neighbor interactions are responsible for the existence of the glacial state.

UR - http://www.scopus.com/inward/record.url?scp=11444256149&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=11444256149&partnerID=8YFLogxK

U2 - 10.1021/jp046762o

DO - 10.1021/jp046762o

M3 - Article

AN - SCOPUS:11444256149

VL - 108

SP - 20076

EP - 20082

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 52

ER -