Compressibility of Hexagonal Selenium by X-Ray and Neutron Diffraction

McCann, D. R.; Cartz, L.; Schmunk, R.E.; Harker, Y.D.

doi:10.1063/1.1661336

Cited by 69 publications

(41 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Clearly, materials that expand with decreasing temperature along a specific direction while contracting overall would, in principle, be able to reduce their volume under increasing hydrostatic pressure while expanding along the same direction that exhibits NTE. This is seen in (for example) Se (5,19), ␣Ј-NaV 2 O 5 along the orthorhombic a and b directions (7,32) The thermodynamic formalisms that relate thermal expansion to compressibility in anisotropic materials are well-understood (36). Omitting shear terms, we have…”

Section: Discussionmentioning

confidence: 99%

Large negative linear compressibility of Ag ₃ [Co(CN) ₆ ]

Goodwin

Keen

Tucker

2008

Proc. Natl. Acad. Sci. U.S.A.

233

266

View full text Add to dashboard Cite

Silver(I) hexacyanocobaltate(III), Ag3[Co(CN)6], shows a large negative linear compressibility (NLC, linear expansion under hydrostatic pressure) at ambient temperature at all pressures up to our experimental limit of 7.65(2) GPa. This behavior is qualitatively unaffected by a transition at 0.19 GPa to a new phase Ag 3[Co(CN)6]-II, whose structure is reported here. The high-pressure phase also shows anisotropic thermal expansion with large uniaxial negative thermal expansion (NTE, expansion on cooling). In both phases, the NLC/NTE effect arises as the rapid compression/contraction of layers of silver atoms-weakly bound via argentophilic interactions-is translated via flexing of the covalent network lattice into an expansion along a perpendicular direction. It is proposed that framework materials that contract along a specific direction on heating while expanding macroscopically will, in general, also expand along the same direction under hydrostatic pressure while contracting macroscopically.negative linear compression ͉ negative thermal expansion ͉ high-pressure ͉ framework materials ͉ flexibility N egative linear compressibility (NLC), whereby a material expands along a specific direction on increasing hydrostatic pressure, is a very unusual effect. Indeed in a study of elastic constant data from 500 noncubic crystal phases, only 13 displayed NLC, and of those, 11 structures were of monoclinic or lower symmetry (1). Despite its rarity, NLC is a highly attractive mechanical property, with a key application being the development of effectively incompressible optical materials (1, 2). Such materials could be used in high-pressure environments, such as in optical telecommunications devices that must function at deep-sea pressures Ͼ1,000 atm. NLC also offers a means of producing ultrasensitive pressure detectors, such as interferometric optical sensors for sonar and aircraft altitude measurements. The effect is also often coupled to so-called ''auxetic'' behavior, which is itself being used to improve shock resistance in, e.g., body armor (3).Of the few known examples among inorganic materials, the most pronounced NLC effects have been reported for LaNbO 4 (4), elemental Se (5), the BXO 4 (X ϭ P, As) family (6), and the spin-Peierls compound ␣Ј-NaV 2 O 5 (7). In some other cases, transient NLC behavior may occur only at pressures just above a strain-induced phase transition to a structure of lower symmetry (e.g., refs. 8 and 9), or as a result of an uptake of additional interstitial molecules (10, 11).One fundamental barrier to the practical application of NLC is that its magnitude is generally much smaller than the ''normal'' (positive) compressibilities of standard materials.* By convention, linear compressibility is defined as the relative rate at which a given dimension ᐉ decreases with pressure (at constant temperature): K ᐉ ϭ Ϫ(Ѩlnᐉ/Ѩp) T . Typical values for crystalline materials lie in the range K ᐉ Ӎ 5-20 TPa Ϫ1 (12) (i.e., their linear dimensions decrease by Ϸ1% for each GPa increase in pressure). In cont...

show abstract

Section: Discussionmentioning

confidence: 99%

Large negative linear compressibility of Ag ₃ [Co(CN) ₆ ]

Goodwin

Keen

Tucker

2008

Proc. Natl. Acad. Sci. U.S.A.

233

266

View full text Add to dashboard Cite

show abstract

“…Trigonal selenium shows a rich phase transition sequence at room temperature, similar to that of Te, but with higher transition pressure [6,9,10,[12][13][14][15][16][17][18][19][20][21]. Se-I is reported to transform at 14 GPa to Se-II with a C-face-centered monoclinic structure [10].…”

Section: High-pressure Transition Sequence Of S Se and Tementioning

confidence: 97%

Crystal structure of sulfur and selenium at pressures up to 160 GPa

Degtyareva¹,

Gregoryanz²,

Mao³

et al. 2005

High Pressure Research

View full text Add to dashboard Cite

Using advanced in situ X-ray diffraction techniques at high pressures and temperatures, we have resolved the long-standing problem of the phase transition sequence of sulfur in its non-metallic state. Our data show that there are only two phases of sulfur stable between 1.5 GPa and pressure of metallization of 86 GPa, S-II with triangular chain structure and S-III with novel squared chain structure. The same squared chain structure is formed in the heavier group-VI element Se at pressures of 20 GPa and temperatures of 450 K. Our X-ray diffraction data on metallic phases of sulfur above 83 GPa show that the S-IV phase has an incommensurately modulated monoclinic structure, the same as recently reported modulated structures of Te-III and Se-IV. S-IV is shown to transform to primitive rhombohedral β-Po phase at 153(3) GPa, the same transition is found in Se at pressure of around 80 GPa.

show abstract

“…1,9 Furthermore, systematic computational procedures gradually applied to predict or design new NLC materials. 24−29 Although these models and mechanisms provide the accesses to seeking new NLC materials, the studies of NLC are confined in simple inorganic compounds, 15 3 In the past few years, primary efforts were concentrated on improving the magnitude of NLC materials, 2 but few efforts were on extending the range. 23 Comparing with inorganic materials, organic materials are soft compounds for the characteristic weak intermolecular interactions in their structure.…”

mentioning

confidence: 99%

Negative Linear Compressibility in Organic Mineral Ammonium Oxalate Monohydrate with Hydrogen Bonding Wine-Rack Motifs

Qiao

Wang

Yuan

et al. 2015

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

Negative linear compressibility (NLC) is a relatively uncommon phenomenon and rarely studied in organic systems. Here we provide the direct evidence of the persistent NLC in organic mineral ammonium oxalate monohydrate under high pressure using synchrotron X-ray powder diffraction, Raman spectroscopy and density functional theory (DFT) calculation. Synchrotron X-ray powder diffraction measurement reveals that ammonium oxalate monohydrate shows both positive and negative linear compressibility along b-axis before 11.5 GPa. The red shift of the external Raman modes and abnormal changes of several selected internal modes in high-pressure Raman spectra further confirmed the NLC. DFT calculations demonstrate that the N-H···O hydrogen bonding "wine-rack" motifs result in the NLC along b-axis in ammonium oxalate monohydrate. We anticipate the high-pressure study of ammonium oxalate monohydrate may represent a promising strategy for accelerating the pace of exploitation and improvement of NLC materials especially in organic systems.

show abstract

Compressibility of Hexagonal Selenium by X-Ray and Neutron Diffraction

Cited by 69 publications

References 10 publications

Large negative linear compressibility of Ag ₃ [Co(CN) ₆ ]

Large negative linear compressibility of Ag ₃ [Co(CN) ₆ ]

Crystal structure of sulfur and selenium at pressures up to 160 GPa

Negative Linear Compressibility in Organic Mineral Ammonium Oxalate Monohydrate with Hydrogen Bonding Wine-Rack Motifs

Contact Info

Product

Resources

About

Compressibility of Hexagonal Selenium by X-Ray and Neutron Diffraction

Cited by 69 publications

References 10 publications

Large negative linear compressibility of Ag 3 [Co(CN) 6 ]

Large negative linear compressibility of Ag 3 [Co(CN) 6 ]

Crystal structure of sulfur and selenium at pressures up to 160 GPa

Negative Linear Compressibility in Organic Mineral Ammonium Oxalate Monohydrate with Hydrogen Bonding Wine-Rack Motifs

Contact Info

Product

Resources

About

Large negative linear compressibility of Ag ₃ [Co(CN) ₆ ]

Large negative linear compressibility of Ag ₃ [Co(CN) ₆ ]