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Title: Chemical bonding in hydrogen and lithium under pressure

Though hydrogen and lithium have been assigned a common column of the periodic table, their crystalline states under common conditions are drastically different: the former at temperatures where it is crystalline is a molecular insulator, whereas the latter is a metal that takes on simple structures. On compression, however, the two come to share some structural and other similarities associated with the insulator-to-metal and metal-to-insulator transitions, respectively. To gain a deeper understanding of differences and parallels in the behaviors of compressed hydrogen and lithium, we performed an ab initio comparative study of these systems in selected identical structures. Both elements undergo a continuous pressure-induced s-p electronic transition, though this is at a much earlier stage of development for H. The valence charge density accumulates in interstitial regions in Li but not in H in structures examined over the same range of compression. Moreover, the valence charge density distributions or electron localization functions for the same arrangement of atoms mirror each other as one proceeds from one element to the other. Application of the virial theorem shows that the kinetic and potential energies jump across the first-order phase transitions in H and Li are opposite in sign because of non-local effectsmore » in the Li pseudopotential. Finally, the common tendency of compressed H and Li to adopt three-fold coordinated structures as found is explained by the fact that such structures are capable of yielding a profound pseudogap in the electronic densities of states at the Fermi level, thereby reducing the kinetic energy. These results have implications for the phase diagrams of these elements and also for the search for new structures with novel properties.« less
Authors:
;  [1] ;  [2] ;  [3]
  1. Geophysical Laboratory, Carnegie Institution of Washington, 5251 Broad Branch Rd. NW, Washington, DC 20015 (United States)
  2. Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853 (United States)
  3. Laboratory of Atomic and Solid State Physics and Cornell Center for Materials Research, Cornell University, Clark Hall, Ithaca, New York 14853 (United States)
Publication Date:
OSTI Identifier:
22493515
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 6; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ATOMS; CHARGE DENSITY; CHEMICAL BONDS; COMPRESSION; CRYSTALS; DENSITY OF STATES; ELECTRONS; FERMI LEVEL; GAIN; HYDROGEN; KINETIC ENERGY; LITHIUM; PHASE DIAGRAMS; PHASE TRANSFORMATIONS; POTENTIAL ENERGY; POTENTIALS; VALENCE; VIRIAL THEOREM