Four-body interaction energy for compressed solid krypton from quantum theory.
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Abstract | :
The importance of the four-body contribution in compressed solid krypton was first evaluated using the many-body expansion method and the coupled cluster theory with full single and double excitations plus perturbative treatment of triples. All different four-atom clusters existing in the first- and second-nearest neighbor shells of face-centered cubic krypton were considered, and both self-consistent-field Hartree-Fock and correlation parts of the four-body interaction were accurately determined from the ambient conditions up to eightfold volume compression. We find that the four-body interaction energy is negative at compression ratio lower than 2, where the dispersive forces play a dominant role. With increasing the compression, the four-body contribution becomes repulsive and significantly cancels the over-softening effects of the three-body potential. The obtained equation of state (EOS) was compared with the experiments and the density-functional theory calculations. It shows that combination of the four-body effects with two- and three-body interactions leads to an excellent agreement with EOS measurements throughout the whole experimental range 0-130 GPa, and extends the prediction to 300 GPa. |
Year of Publication | :
2012
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Journal | :
The Journal of chemical physics
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Volume | :
137
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Issue | :
4
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Number of Pages | :
044108
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Date Published | :
2012
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ISSN Number | :
0021-9606
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URL | :
https://dx.doi.org/10.1063/1.4737183
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DOI | :
10.1063/1.4737183
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Short Title | :
J Chem Phys
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