Structure, thermodynamics, and diffusion in CaAl2Si2O8 liquid from first-principles molecular dynamics

We have performed first-principles molecular dynamics simulations of CaAl2Si2O8 (anorthite) liquid at pressures up to 120 GPa and temperatures of 3000, 4000 and 6000 K. At the lowest degrees of compression the liquid is seen to accommodate changes in density through decreasing the abundance of 3- and 4-membered rings, while increases in coordination of network forming cations take effect at somewhat higher degrees of compression. Results are fit to a fundamental thermodynamic relation with 4th order finite strain and 1st order thermal variable expansions. Upon compression by a factor of two, the Gruneisen parameter (gamma) is found to increase continuously from 0.35 to 1.10. Weak temperature dependence in gamma is thermodynamically consistent with a slight decrease in isochoric heat capacity (C-V), for which values of between 4.4 and 5.2 Nk(B) are obtained, depending on the temperature. Pressure and temperature dependence of self-diffusivities is found to be well represented by an Arrhenius relation, except at 3000 K and pressures lower than 5 GPa, where self-diffusivities of Si, Al, and O increase with pressure. Analysis of the lifetimes of individual coordination species reveals that this phenomenon arises due to the disproportionately high stability of 4-fold coordinated Si, and to a lesser extent 4-fold coordinated Al. Our results represent a marked improvement in accuracy and reliability in describing the physics of CaAl2Si2O8 liquid at deep mantle pressures, pointing the way to a general thermodynamic model of melts at extreme pressures and temperatures relevant to planetary-scale magma oceans and deep mantle partial melting. (C) 2010 Elsevier Ltd. All rights reserved.