Local Structure and Dynamics in MPt(CN) 6 Prussian Blue Analogues
We use a combination of X-ray pair distribution function (PDF) measurements, lattice dynamical calculations, and ab initio density functional theory (DFT) calculations to study the local structure and dynamics in various MPt(CN)6 Prussian blue analogues. In order to link directly the local distorti...
| Main Authors: | , , , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
American Chemical Society
2024
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| _version_ | 1826313203400835072 |
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| author | Harbourne, EA Barker, H Guéroult, Q Cattermull, J Nagle-Cocco, LAV Roth, N Evans, JSO Keen, DA Goodwin, AL |
| author_facet | Harbourne, EA Barker, H Guéroult, Q Cattermull, J Nagle-Cocco, LAV Roth, N Evans, JSO Keen, DA Goodwin, AL |
| author_sort | Harbourne, EA |
| collection | OXFORD |
| description | We use a combination of X-ray pair distribution function (PDF) measurements, lattice dynamical calculations, and ab initio density functional theory (DFT) calculations to study the local structure and dynamics in various MPt(CN)6 Prussian blue analogues. In order to link directly the local distortions captured by the PDF with the lattice dynamics of this family, we develop and apply a new “interaction-space” PDF refinement approach. This approach yields effective harmonic force constants, from which the (experiment-derived) low-energy phonon dispersion relations can be approximated. Calculation of the corresponding Grüneisen parameters allows us to identify the key modes responsible for negative thermal expansion (NTE) as arising from correlated tilts of coordination octahedra. We compare our results against the phonon dispersion relations determined using DFT calculations, which identify the same NTE mechanism. |
| first_indexed | 2024-09-25T04:09:25Z |
| format | Journal article |
| id | oxford-uuid:beaecddc-d937-4508-ab3b-ace0950efe80 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-09-25T04:09:25Z |
| publishDate | 2024 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:beaecddc-d937-4508-ab3b-ace0950efe802024-06-12T20:05:46ZLocal Structure and Dynamics in MPt(CN) 6 Prussian Blue AnaloguesJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:beaecddc-d937-4508-ab3b-ace0950efe80EnglishJisc Publications RouterAmerican Chemical Society2024Harbourne, EABarker, HGuéroult, QCattermull, JNagle-Cocco, LAVRoth, NEvans, JSOKeen, DAGoodwin, ALWe use a combination of X-ray pair distribution function (PDF) measurements, lattice dynamical calculations, and ab initio density functional theory (DFT) calculations to study the local structure and dynamics in various MPt(CN)6 Prussian blue analogues. In order to link directly the local distortions captured by the PDF with the lattice dynamics of this family, we develop and apply a new “interaction-space” PDF refinement approach. This approach yields effective harmonic force constants, from which the (experiment-derived) low-energy phonon dispersion relations can be approximated. Calculation of the corresponding Grüneisen parameters allows us to identify the key modes responsible for negative thermal expansion (NTE) as arising from correlated tilts of coordination octahedra. We compare our results against the phonon dispersion relations determined using DFT calculations, which identify the same NTE mechanism. |
| spellingShingle | Harbourne, EA Barker, H Guéroult, Q Cattermull, J Nagle-Cocco, LAV Roth, N Evans, JSO Keen, DA Goodwin, AL Local Structure and Dynamics in MPt(CN) 6 Prussian Blue Analogues |
| title | Local Structure and Dynamics in MPt(CN) 6 Prussian Blue Analogues |
| title_full | Local Structure and Dynamics in MPt(CN) 6 Prussian Blue Analogues |
| title_fullStr | Local Structure and Dynamics in MPt(CN) 6 Prussian Blue Analogues |
| title_full_unstemmed | Local Structure and Dynamics in MPt(CN) 6 Prussian Blue Analogues |
| title_short | Local Structure and Dynamics in MPt(CN) 6 Prussian Blue Analogues |
| title_sort | local structure and dynamics in mpt cn 6 prussian blue analogues |
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