### Temperature dependence of the Fe²⁺ Mössbauer parameters in triphylite (LiFePO₄)

Toon Van Alboom UGent, Eddy De Grave UGent (2011) 96(2-3). p.408-416
abstract
The ferrous Mössbauer parameters are determined for synthetic triphylite (LiFePO4) over a wide temperature range between 8 and 900 K. A sharp magnetic order-disorder transition is observed at (52.5 ± 0.5) K. In the paramagnetic state, the Mössbauer spectra are adequately analyzed by one Fe2+ quadrupole doublet with a narrow line width of 0.285 mm/s at room temperature. In the magnetic state, the spectra show up to eight absorption lines, which is typical for Fe2+. These spectra are analyzed through diagonalization of the full nuclear-interaction hamiltonian. The hyperfine field Bhf is found to be collinear to the local principal axis of the electric field gradient (EFG) tensor. The saturation value for Bhf is 125.5 kOe. For temperatures below 52 K, the adjusted value for the asymmetry parameter of the EFG is η ≈ 0.8 and for the quadrupole splitting ΔEQ = 3.06 mm/s. This latter value is perfectly in line with the value at 80 K (paramagnetic regime). The temperature dependence of the quadrupole splitting is interpreted within the 5D orbital energy level scheme of Fe2+ by a crystal field calculation based on the point symmetry of the Fe2+ site in triphylite. The variation of the hyperfine field with temperature is interpreted within the molecular field approximation, however, taking exchange magnetostriction into account. From the temperature dependence of the isomer shift the characteristic Mössbauer temperature ΘM is determined to be 418 K and the intrinsic isomer shift δI = 1.46 mm/s. From these, the Mössbauer fraction at room temperature is calculated to be 0.785.
author
organization
alternative title
Temperature dependence of the Fe2+ Mossbauer parameters in triphylite (LiFePO4)
year
type
journalArticle (original)
publication status
published
subject
keyword
SPECTROSCOPY, SPECTRA, HYPERFINE INTERACTIONS, crystal field calculation, liquid helium, hyperfine field, quadrupole interaction, isomer shift, Triphylite, IONS, Mossbauer, FEPO4, BATTERIES, FIELD, ENERGY, FE-57, FRACTIONS
journal title
AMERICAN MINERALOGIST
Am. Miner.
volume
96
issue
2-3
pages
408 - 416
Web of Science type
Article
Web of Science id
000287336200021
JCR category
MINERALOGY
JCR impact factor
2.169 (2011)
JCR rank
6/26 (2011)
JCR quartile
1 (2011)
ISSN
0003-004X
DOI
10.213/am.2011.3630
language
English
UGent publication?
yes
classification
A1
I have transferred the copyright for this publication to the publisher
id
1182712
handle
http://hdl.handle.net/1854/LU-1182712
date created
2011-03-08 09:16:33
date last changed
2016-12-19 15:45:50
@article{1182712,
abstract     = {The ferrous M{\"o}ssbauer parameters are determined for synthetic triphylite (LiFePO4) over a wide temperature range between 8 and 900 K. A sharp magnetic order-disorder transition is observed at (52.5 {\textpm} 0.5) K. In the paramagnetic state, the M{\"o}ssbauer spectra are adequately analyzed by one Fe2+ quadrupole doublet with a narrow line width of 0.285 mm/s at room temperature. In the magnetic state, the spectra show up to eight absorption lines, which is typical for Fe2+. These spectra are analyzed through diagonalization of the full nuclear-interaction hamiltonian. The hyperfine field Bhf is found to be collinear to the local principal axis of the electric field gradient (EFG) tensor. The saturation value for Bhf is 125.5 kOe. For temperatures below 52 K, the adjusted value for the asymmetry parameter of the EFG is \ensuremath{\eta} \ensuremath{\asymp} 0.8 and for the quadrupole splitting \ensuremath{\Delta}EQ = 3.06 mm/s. This latter value is perfectly in line with the value at 80 K (paramagnetic regime). The temperature dependence of the quadrupole splitting is interpreted within the 5D orbital energy level scheme of Fe2+ by a crystal field calculation based on the point symmetry of the Fe2+ site in triphylite. The variation of the hyperfine field with temperature is interpreted within the molecular field approximation, however, taking exchange magnetostriction into account. From the temperature dependence of the isomer shift the characteristic M{\"o}ssbauer temperature \ensuremath{\Theta}M is determined to be 418 K and the intrinsic isomer shift \ensuremath{\delta}I = 1.46 mm/s. From these, the M{\"o}ssbauer fraction at room temperature is calculated to be 0.785.},
author       = {Van Alboom, Toon and De Grave, Eddy and Wohlfahrt-Mehrens, Margret},
issn         = {0003-004X},
journal      = {AMERICAN MINERALOGIST},
keyword      = {SPECTROSCOPY,SPECTRA,HYPERFINE INTERACTIONS,crystal field calculation,liquid helium,hyperfine field,quadrupole interaction,isomer shift,Triphylite,IONS,Mossbauer,FEPO4,BATTERIES,FIELD,ENERGY,FE-57,FRACTIONS},
language     = {eng},
number       = {2-3},
pages        = {408--416},
title        = {Temperature dependence of the Fe{\texttwosuperior}\unmatched{207a} M{\"o}ssbauer parameters in triphylite (LiFePO\unmatched{2084})},
url          = {http://dx.doi.org/10.213/am.2011.3630},
volume       = {96},
year         = {2011},
}


Chicago
Van Alboom, Toon, Eddy De Grave, and Margret Wohlfahrt-Mehrens. 2011. “Temperature Dependence of the Fe2+ Mössbauer Parameters in Triphylite (LiFePO₄).” American Mineralogist 96 (2-3): 408–416.
APA
Van Alboom, T., De Grave, E., & Wohlfahrt-Mehrens, M. (2011). Temperature dependence of the Fe2+ Mössbauer parameters in triphylite (LiFePO₄). AMERICAN MINERALOGIST, 96(2-3), 408–416.
Vancouver
1.
Van Alboom T, De Grave E, Wohlfahrt-Mehrens M. Temperature dependence of the Fe2+ Mössbauer parameters in triphylite (LiFePO₄). AMERICAN MINERALOGIST. 2011;96(2-3):408–16.
MLA
Van Alboom, Toon, Eddy De Grave, and Margret Wohlfahrt-Mehrens. “Temperature Dependence of the Fe2+ Mössbauer Parameters in Triphylite (LiFePO₄).” AMERICAN MINERALOGIST 96.2-3 (2011): 408–416. Print.