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Title: The incommensurately modulated NiGe{sub 1-x}P{sub x}, {approx}0.3=<x=<{approx}0.7, solid solution: The 'missing link' between the NiP and MnP structure types

Abstract

The (3+1)-d incommensurately modulated structures of four members of the NiGe{sub 1-x}P{sub x} solid solution field have been successfully refined from X-ray powder diffraction data (R{sub w}(all)/R{sub wp}=2.13/3.92; 1.52/4.25; 1.27/3.44 and 2.00/4.03 for x=0.4, 0.5, 0.6 and 0.7, respectively). The 4-d superspace group symmetry is Amam(00{gamma})s00 (Z=4; a=5.0468(2), 5.0188(2), 4.9796(2) and 4.9651(1)A; b=6.0636(3), 6.0576(2), 6.0183(2) and 6.0031(1)A; c=3.4877(2), 3.4812(2), 3.4593(1) and 3.45442(7)A; {gamma}=0.7769(2), 0.7467(1), 0.7241(1) and 0.7046(1) for x=0.4, 0.5, 0.6 and 0.7, respectively). The underlying average structure is of NiAs type while the (in general) incommensurate primary modulation wave-vector, {gamma}c{sup *}, varies continuously and smoothly with composition. The two largest amplitude displacive atomic modulation functions (AMFs), for all samples, were the Ni displacement along b AMF and the Ge/P displacement along a AMF. The refined amplitude of the former was found to systematically increase with P content from 0.215A for NiGe{sub 0.6}P{sub 0.4} to 0.294A for NiGe{sub 0.3}P{sub 0.7} while the magnitude of the latter was found to increase with P content from 0.177A for NiGe{sub 0.6}P{sub 0.4} to 0.253A for NiGe{sub 0.3}P{sub 0.7}. These displacive shifts significantly modulate the local crystal chemistry i.e. the local interatomic distances and co-ordination polyhedra. This continuously variable, incommensurately modulated, intermediate structure typemore » is shown to provide a natural link or bridge between the two extreme end-member structures i.e. NiGe (of MnP structure type) and NiP by simply choosing the commensurate options with {gamma}=1 and 12 respectively.« less

Authors:
 [1];  [2];  [3]
  1. Research School of Chemistry, Australian National University, Canberra, ACT 0200 (Australia), E-mail: ankie.larsson@anu.edu.au
  2. Lehrstuhl fuer Festkoerperchemie, Instituet for Physik, Universitaet Augsburg, Universitaetsstrasse 1, D-86159 Augsburg (Germany)
  3. Research School of Chemistry, Australian National University, Canberra, ACT 0200 (Australia)
Publication Date:
OSTI Identifier:
21015751
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 3; Other Information: DOI: 10.1016/j.jssc.2007.01.006; PII: S0022-4596(07)00023-0; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; GERMANIDES; INTERATOMIC DISTANCES; INTERMEDIATE STRUCTURE; NICKEL PHOSPHIDES; SOLID SOLUTIONS; SYMMETRY; X-RAY DIFFRACTION

Citation Formats

Larsson, A.-K., Garcia-Garcia, F.J., and Withers, R.L. The incommensurately modulated NiGe{sub 1-x}P{sub x}, {approx}0.3=<x=<{approx}0.7, solid solution: The 'missing link' between the NiP and MnP structure types. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2007.01.006.
Larsson, A.-K., Garcia-Garcia, F.J., & Withers, R.L. The incommensurately modulated NiGe{sub 1-x}P{sub x}, {approx}0.3=<x=<{approx}0.7, solid solution: The 'missing link' between the NiP and MnP structure types. United States. doi:10.1016/j.jssc.2007.01.006.
Larsson, A.-K., Garcia-Garcia, F.J., and Withers, R.L. Thu . "The incommensurately modulated NiGe{sub 1-x}P{sub x}, {approx}0.3=<x=<{approx}0.7, solid solution: The 'missing link' between the NiP and MnP structure types". United States. doi:10.1016/j.jssc.2007.01.006.
@article{osti_21015751,
title = {The incommensurately modulated NiGe{sub 1-x}P{sub x}, {approx}0.3=<x=<{approx}0.7, solid solution: The 'missing link' between the NiP and MnP structure types},
author = {Larsson, A.-K. and Garcia-Garcia, F.J. and Withers, R.L.},
abstractNote = {The (3+1)-d incommensurately modulated structures of four members of the NiGe{sub 1-x}P{sub x} solid solution field have been successfully refined from X-ray powder diffraction data (R{sub w}(all)/R{sub wp}=2.13/3.92; 1.52/4.25; 1.27/3.44 and 2.00/4.03 for x=0.4, 0.5, 0.6 and 0.7, respectively). The 4-d superspace group symmetry is Amam(00{gamma})s00 (Z=4; a=5.0468(2), 5.0188(2), 4.9796(2) and 4.9651(1)A; b=6.0636(3), 6.0576(2), 6.0183(2) and 6.0031(1)A; c=3.4877(2), 3.4812(2), 3.4593(1) and 3.45442(7)A; {gamma}=0.7769(2), 0.7467(1), 0.7241(1) and 0.7046(1) for x=0.4, 0.5, 0.6 and 0.7, respectively). The underlying average structure is of NiAs type while the (in general) incommensurate primary modulation wave-vector, {gamma}c{sup *}, varies continuously and smoothly with composition. The two largest amplitude displacive atomic modulation functions (AMFs), for all samples, were the Ni displacement along b AMF and the Ge/P displacement along a AMF. The refined amplitude of the former was found to systematically increase with P content from 0.215A for NiGe{sub 0.6}P{sub 0.4} to 0.294A for NiGe{sub 0.3}P{sub 0.7} while the magnitude of the latter was found to increase with P content from 0.177A for NiGe{sub 0.6}P{sub 0.4} to 0.253A for NiGe{sub 0.3}P{sub 0.7}. These displacive shifts significantly modulate the local crystal chemistry i.e. the local interatomic distances and co-ordination polyhedra. This continuously variable, incommensurately modulated, intermediate structure type is shown to provide a natural link or bridge between the two extreme end-member structures i.e. NiGe (of MnP structure type) and NiP by simply choosing the commensurate options with {gamma}=1 and 12 respectively.},
doi = {10.1016/j.jssc.2007.01.006},
journal = {Journal of Solid State Chemistry},
number = 3,
volume = 180,
place = {United States},
year = {Thu Mar 15 00:00:00 EDT 2007},
month = {Thu Mar 15 00:00:00 EDT 2007}
}