Density functional calculations of surface free energies.
We propose a general method of thermodynamic integration to find the free energy of a surface, where our integration parameter is taken to be the strain on the unit cell of the system (which in the example presented in this paper is simply the extension of the unit cell along the normal to the surface), and the integration is performed over the thermal average stress from a molecular dynamics run. In order to open up a vacuum gap in a continuous and reversible manner, an additional control interaction has been introduced. We also use temperature integration to find a linear relation for the temperature dependence of the free surface energy. These methods have been applied to the titanium dioxide (110) surface, using first principles density functional theory. A proof of principle calculation for zero temperature shows excellent agreement between the integral calculation and the difference in energy calculated by the DFT program. Calculations that have been performed at 295 and 1000 K give excellent agreement between the two integration methods.
Fox
H
H
Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, UK. h.fox@ucl.ac.uk
Horsfield
A P
AP
Gillan
M J
MJ