TY  - JOUR
AU  - Ballone, P.
AU  - Jones, G. J.
TI  - A reactive force field simulation of liquid-liquid phase transitions in phosphorus
JO  - The journal of chemical physics
VL  - 121
SN  - 0021-9606
CY  - Melville, NY
PB  - American Institute of Physics
M1  - PreJuSER-41883
SP  - 8147 - 8157
PY  - 2004
N1  - Record converted from VDB: 12.11.2012
AB  - A force field model of phosphorus has been developed based on density functional (DF) computations and experimental results, covering low energy forms of local tetrahedral symmetry and more compact (simple cubic) structures that arise with increasing pressure. Rules tailored to DF data for the addition, deletion, and exchange of covalent bonds allow the system to adapt the bonding configuration to the thermodynamic state. Monte Carlo simulations in the N-P-T ensemble show that the molecular (P(4)) liquid phase, stable at low pressure P and relatively low temperature T, transforms to a polymeric (gel) state on increasing either P or T. These phase changes are observed in recent experiments at similar thermodynamic conditions, as shown by the close agreement of computed and measured structure factors in the molecular and polymer phases. The polymeric phase obtained by increasing pressure has a dominant simple cubic character, while the polymer obtained by raising T at moderate pressure is tetrahedral. Comparison with DF results suggests that the latter is a semiconductor, while the cubic form is metallic. The simulations show that the T-induced polymerization is due to the entropy of the configuration of covalent bonds, as in the polymerization transition in sulfur. The transition observed with increasing P is the continuation at high T of the black P to arsenic (A17) structure observed in the solid state, and also corresponds to a semiconductor to metal transition.
KW  - J (WoSType)
LB  - PUB:(DE-HGF)16
C6  - pmid:15485279
UR  - <Go to ISI:>//WOS:000224456500069
DO  - DOI:10.1063/1.1801271
UR  - https://juser.fz-juelich.de/record/41883
ER  -