Electronic-enthalpy functional for finite systems under pressure.
We introduce the notion of electronic enthalpy for first-principles structural and dynamical calculations of finite systems under pressure. An external pressure field is allowed to act directly on the electronic structure of the system studied via the ground-state minimization of the functional E+PV(q), where V(q) is the quantum volume enclosed by a charge isosurface. The Hellmann-Feynman theorem applies, and assures that the ionic equations of motion follow an isoenthalpic dynamics. No pressurizing medium is explicitly required, while coatings of environmental ions or ligands can be introduced if chemically relevant. We apply this novel approach to the study of group-IV nanoparticles during a shock wave, highlighting the significant differences in the plastic or elastic response of the diamond cage under load, and their potential use as novel nanostructured impact-absorbing materials.
Cococcioni
Matteo
M
Department of Materials Science and Engineering, and Institute for Soldier Nanotechnologies, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA.
Mauri
Francesco
F
Ceder
Gerbrand
G
Marzari
Nicola
N