Polyhydride Explained

A polyhydride or superhydride is a compound that contains an abnormally large amount of hydrogen. This can be described as high hydrogen stoichiometry. Examples include iron pentahydride,, and . By contrast, the more well known lithium hydride only has one hydrogen atom.[1]

Polyhydrides are only known to be stable under high pressure.[1]

Polyhydrides are important because they can form substances with a very high density of hydrogen. They may resemble the elusive metallic hydrogen, but can be made under lower pressures. One possibility is that they could be superconductors. Hydrogen sulfide under high pressures forms units, and can be a superconductor at 203K and a pressure of 1.5 million atmospheres.[1]

Structures

The polyhydrides of alkaline earth and alkali metals contain cage structures. Also hydrogen may be clustered into,, or units. Polyhydrides of transition metals may have the hydrogen atoms arranged around the metal atom. Computations suggest that increasing hydrogen levels will reduce the dimensionality of the metal arrangement, so that layers form separated by hydrogen sheets.[1] The substructure is linear.[2]

would form triangular structures in the hypothetical .[2]

Compounds

When sodium hydride is compressed with hydrogen, and form. These are formed at 30 GPa and 2,100 K.[2]

Heating and compressing a metal with ammonia borane avoids using bulky hydrogen, and produces boron nitride as a decomposition product in addition to the polyhydride.

formulanametemperature°CpressureGPacrystal structurespace groupa Åbcβcell volumeformulaeperunit cellTc KCommentrefs
lithium dihydride27130[3]
Lithium hexahydride
Lithium heptahydride
sodium trihydrideorthorhombicCmcm3.332 Å6.354 Å4.142 Å9087.694
sodium heptahydridemonoclinicCc6.993.5975.54169.465130.5
50022double hexagon[4]
600121
pseudo cubicPmmsemiconductormetallize > 220 GPa[5]
C2/m
138triclinicP1
Barium dodecahydride75pseudo cubic5.435.415.3739.4820K[6] [7]
iron pentahydride120066tetragonalI4/mmm
Sulfur trihydride25150cubicImm203K[8]
Selenium trihydride10[9]
yttrium tetrahydride700160I4/mmm[10]
yttrium hexahydride700160Im-3m224[11] [12]
yttrium nonahydride400237P63/mmc243
Lanthanum decahydride1000170cubicFmm5.095.095.091324250K[13] [14]
Lanthanum decahydride25121HexagonalRm3.673.678.831
Lanthanum undecahydride2150130-160TetragonalP4/nmm168
Lanthanum dodecahydrideCubicinsulating
Lanthanum heptahydride25109monoclinicC2/m6.443.83.6913563.92
Cerium nonahydride93hexagonalP63/mmc3.7115.54333.053100K[15]
Cerium decahydrideFmm115K[16]
Praseodymium nonahydride90-140P63/mmc3.605.4761.555K 9K[17] [18]
Praseodymium nonahydride120F43m4.9812469K
Neodymium tetrahydride85-135tetragonalI4/mmm2.82345,7808[19]
Neodymium heptahydride85-135monoclinicC2/c3.31776.2525.70789.354
Neodymium nonahydride110-130hexagonalP63/mmc3.4585.935
50-130I4/mmm[20]
1600130cubicPmn5.865
Europium nonahydride86-130cubicF3m
Europium nonahydride>130hexagonalP63/mmc
Thorium tetrahydride86I4/mmm2.9034.42157.232[21]
Thorium tetrahydride88trigonalP3215.5003.2986.18
Thorium tetrahydrideorthorhombicFmmm
Thorium hexahydride86-104Cmc2132.36
Thorium nonahydride2100152hexagonalP63/mmc3.7135.54166.20
Thorium decahydride180085-185cubicFmm5.29148.0161
Thorium decahydride<85Immm5.3043.2873.64774.03
Uranium heptahydride200063fccP63/mmc
Uranium octahydride3001-55fccFmm
Uranium nonahydride40-55fccP63/mmc

Predicted

Using computational chemistry many other polyhydrides are predicted, including,[22],[23],[23],[24],,,[22],,[25],[26],,,[27],[28],,[22],,,[29] and,[30],,,[31],,,,,[32],,, and,[33],,,,[34],[35],,[22],,,[36],[37] (subsequently discovered),[22],[38] (although may be stable instead)[39],,[40],,,[41],[42],[43],,[44],,[22],,[22],,,,[45],,,,,[22], .[46]

Among the transition elements, in a C2/m structure around 200 GPa is predicted to have a superconducting transition temperature of 71.4 K. in a P63/mmm space group has a lower transition temperature.[47]

Properties

Superconduction

Under suitably high pressures polyhydrides may become superconducting. Characteristics of substances that are predicted to have high superconducting temperatures are a high phonon frequency, which will happen for light elements, and strong bonds. Hydrogen is the lightest and so will have the highest frequency of vibration. Even changing the isotope to deuterium will lower the frequency and lower the transition temperature. Compounds with more hydrogen will resemble the predicted metallic hydrogen. However, superconductors also tend to be substances with high symmetry and also need the electrons not to be locked into molecular subunits, and require large numbers of electrons in states near the Fermi level. There should also be electron-phonon coupling which happens when the electric properties are tied to the mechanical position of the hydrogen atoms.[48] [49] [50] The highest superconduction critical temperatures are predicted to be in groups 3 and 3 of the periodic table. Late transitions elements, heavy lanthanides or actinides have extra d- or f-electrons that interfere with superconductivity.[51]

For example, lithium hexahydride is predicted to lose all electrical resistance below 38 K at a pressure of 150 GPa. The hypothetical has a predicted superconducting transition temperature at 31 K at 200 GPa.[52] is predicted to have a Tc of 400 K around 300 GPa.[53] could have a Tc of 260 K at 120 GPa. doped is also predicted to have a transition temperature above the 203 K measured for (contaminated with solid sulfur).[54] Rare earth and actinide polyhydrides may also have highish transition temperatures, for example, with Tc = 241 K.[33], which can be decompressed to room temperature without decomposition, is predicted to have a transition temperature of 193 K.[33], if it could be ever made, is predicted to superconduct at temperatures over 204 K, and would be similarly conducting under lower pressures (150 GPa).[55]

actually is a van der Waals solid with formula with a measured Tc of 105 K under a pressure of 135 GPa.[9]

Ternary superhydrides

Ternary superhydrides open up the possibility of many more formulas.[56] For example, may also be superconducting at high temperatures (200 °C).[57] A compound of lanthanum, boron and hydrogen is speculated to be a "hot" superconductor (550 K).[58] [59] Elements may substitute for others and so modify the properties eg and can be made to have a slightly higher critical temperature than or .[60]

See also

Notes and References

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