The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite

Density functional theory calculations have been used to study the pressure-induced changes of the hydrogen bond of Fe-free orthozoisite and clinozoisite and the concomitant shifts of the OH-stretching frequencies. Two independent parameter-free lattice dynamical calculations have been employed. One...

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Main Authors: Winkler, B., Gale, Julian, Refson, K., Wilson, D., Milman, V.
Format: Journal Article
Published: Springer-Verlag 2008
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/6897
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author Winkler, B.
Gale, Julian
Refson, K.
Wilson, D.
Milman, V.
author_facet Winkler, B.
Gale, Julian
Refson, K.
Wilson, D.
Milman, V.
author_sort Winkler, B.
building Curtin Institutional Repository
collection Online Access
description Density functional theory calculations have been used to study the pressure-induced changes of the hydrogen bond of Fe-free orthozoisite and clinozoisite and the concomitant shifts of the OH-stretching frequencies. Two independent parameter-free lattice dynamical calculations have been employed. One was based on a planewave basis set in conjunction with norm-conserving pseudopotentials and a density functional perturbation theory approach, while the other used a localised basis set and a finite displacement algorithm for the lattice dynamical calculations. Both models confirm the unusually large pressure-induced red-shift found experimentally ( 33.89 cm 1/GPa) in orthozoisite, while the pressureinduced shifts in clinozoisite are much smaller ( 5 to 9 cm 1/GPa). The atomistic model calculations show that in orthozoisite the nearly linear O H_O arrangement is compressed by about 8% on a pressure increase to 10 GPa,while concomitantly the O H distance is significantly elongated (by 2.5% at 10 GPa). In clinozoisite, the O H_O arrangement is kinked \OHO 166 at ambient conditions and remains kinked at high pressures, while the O-H distance is elongated by only 0.5% at10 GPa. The current calculations confirm that correlations between the distances and dynamics of hydrogen bonds, which have been established at ambient conditions, cannotbe used to infer hydrogen positions at high pressures.
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spelling curtin-20.500.11937-68972018-09-25T01:28:26Z The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite Winkler, B. Gale, Julian Refson, K. Wilson, D. Milman, V. D. lattice dynamics C. Hydrogen bond B. High pressure A. Zoisite Density functional theory calculations have been used to study the pressure-induced changes of the hydrogen bond of Fe-free orthozoisite and clinozoisite and the concomitant shifts of the OH-stretching frequencies. Two independent parameter-free lattice dynamical calculations have been employed. One was based on a planewave basis set in conjunction with norm-conserving pseudopotentials and a density functional perturbation theory approach, while the other used a localised basis set and a finite displacement algorithm for the lattice dynamical calculations. Both models confirm the unusually large pressure-induced red-shift found experimentally ( 33.89 cm 1/GPa) in orthozoisite, while the pressureinduced shifts in clinozoisite are much smaller ( 5 to 9 cm 1/GPa). The atomistic model calculations show that in orthozoisite the nearly linear O H_O arrangement is compressed by about 8% on a pressure increase to 10 GPa,while concomitantly the O H distance is significantly elongated (by 2.5% at 10 GPa). In clinozoisite, the O H_O arrangement is kinked \OHO 166 at ambient conditions and remains kinked at high pressures, while the O-H distance is elongated by only 0.5% at10 GPa. The current calculations confirm that correlations between the distances and dynamics of hydrogen bonds, which have been established at ambient conditions, cannotbe used to infer hydrogen positions at high pressures. 2008 Journal Article http://hdl.handle.net/20.500.11937/6897 10.1007/s00269-007-0195-1 Springer-Verlag fulltext
spellingShingle D. lattice dynamics
C. Hydrogen bond
B. High pressure
A. Zoisite
Winkler, B.
Gale, Julian
Refson, K.
Wilson, D.
Milman, V.
The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite
title The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite
title_full The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite
title_fullStr The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite
title_full_unstemmed The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite
title_short The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite
title_sort influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite
topic D. lattice dynamics
C. Hydrogen bond
B. High pressure
A. Zoisite
url http://hdl.handle.net/20.500.11937/6897