Comparative Study of the High‐Pressure Behavior of As, Sb, and Bi

Abstract

Theory Theory C 1000 Comparative Study of the High-Pressure Behavior of As, Sb, and Bi -[DFT calculations]. -(HAEUSSERMANN*, U.; SOEDERBERG, K.; NORRESTAM, R.; J. Am. Chem. Soc. 124 (2002) 51, 15359-15367; Dep. Inorg. Chem., Arrhenius Lab., Univ. Stockholm, S-106 91 Stockholm, Swed.; Eng.) -Schramke 16-001

Electronic structure and bonding in antimony and its high pressure phases

“…In what follows we will refer to the atoms forming the framework (chain) as host (guest) atoms. The calculated transition pressures, fractional volume changes at the transition and the pressure -volume curves were also in perfect agreement with their experimental counterparts [13,15]. However, even this complicated model did not account for a few weak reflections.…”

“…Some more complex atomic patterns have been found, such as arrangements with incommensurate host-guest sublattices, or with unit cells of more than 50 atoms [4][5][6][7]. In general excellent agreement between experimental and theoretical results has been obtained in the study of the high pressure phases of elemental solids [8][9][10][11][12][13][14]. In general excellent agreement between experimental and theoretical results has been obtained in the study of the high pressure phases of elemental solids [8][9][10][11][12][13][14].…”

“…It is worthwhile to discuss especially this issue in some detail since in some investigations the total energy is decomposed and only the magnitude of a single contribution is taken into account for discussing the stability of a certain crystal structure in comparison to alternative atomic arrangements [13,14]. The most relevant component in this type of approaches is the band energy, defined as the sum of the energies of the occupied states:…”

“…A tetragonal model with space group P4=n containing 10 atoms per cell was suggested in 1990 [18]. However, in the first-principles electronic structure calculations for the Sb-II phase a commensurate structure model approximating the modulated composite was used [13,15]. In what follows we will refer to the atoms forming the framework (chain) as host (guest) atoms.…”

Refinement of the crystal structure of Bi-II, at 2.54 GPa

“…The level of deformation with respect to the rhombohedral phase is definitely higher as supposed previously, which can be illustrated by comparison of the shortest interatomic distances: 1 × 3.156(3) Å, 2 × 3.2073(8) Å, 2 × 3.300(3) Å and 1 × 3.314(3) Å in the present work and 1 × 3.145 Å, 2 × 3.165 Å, 2 × 3.300 Å and 1 × 3.391 Å by applying the atomic coordinates from [1]. This could explain the difficulties to simulate the Bi-I to Bi-II transformation by means of the density functional calculations [5]. With the re-determined atomic parameters, the structure of Bi-II at 2.54 GPa is more distinct from the Bi-I modification, as it could be assumed before.…”