In computer simulations, quantum delocalization of atomic nuclei can be modeled making use of the Path Integral (PI) formulation of quantum statistical mechanics. This approach, however, comes with a large computational cost. By restricting the PI mo
deling to a small region of space, this cost can be significantly reduced. In the present work we derive a Hamiltonian formulation for a bottom-up, theoretically solid simulation protocol that allows molecules to change their resolution from quantum-mechanical to classical and vice versa on the fly, while freely diffusing across the system. This approach renders possible simulations of quantum systems at constant chemical potential. The validity of the proposed scheme is demonstrated by means of simulations of low temperature parahydrogen. Potential future applications include simulations of biomolecules, membranes, and interfaces.
We have developed an efficient scalable kernel method for thermal transport in open systems, with which we have computed the thermal conductance of a junction between bulk silicon and silicon nanowires with diameter up to 10 nm. We have devised scali
ng laws for transmission and reflection spectra, which allow us to predict the thermal resistance of bulk-nanowire interfaces with larger cross sections than those achievable with atomistic simulations. Our results indicate the characteristic size beyond which atomistic systems can be treated accurately by mesoscopic theories.
Understanding the behavior of molecular systems under pressure is a fundamental problem in condensed matter physics. In the case of nitrogen, the determination of the phase diagram and in particular of the melting line, are largely open problems. Two
independent experiments have reported the presence of a maximum in the nitrogen melting curve, below 90 GPa, however the position and the interpretation of the origin of such maximum differ. By means of ab initio molecular dynamics simulations based on density functional theory and thermodynamic integration techniques, we have determined the phase diagram of nitrogen in the range between 20 and 100 GPa. We find a maximum in the melting line, related to a transformation in the liquid, from molecular N_2 to polymeric nitrogen accompanied by an insulator-to-metal transition.
We present computer simulations of liquid and solid phases of condensed methane at pressures below 25 GPa, between 150 and 300 K, where no appreciable molecular dissociation occurs. We used molecular dynamics (MD) and metadynamics techniques, and emp
irical potentials in the rigid molecule approximation, whose validity was confirmed a posteriori by carrying out it ab initio MD simulations for selected pressure and temperature conditions. Our results for the melting line are in satisfactory agreement with existing measurements. We find that the fcc crystal transforms into a hcp structure with 4 molecules per unit cell (B phase) at about 10 GPa and 150 K, and that the B phase transforms into a monoclinic high pressure phase above 20 GPa. Our results for solid/solid phase transitions are consistent with those of Raman studies but the phase boundaries estimated in our calculations are at higher pressure than those inferred from spectroscopic data.
We present a new molecular dynamics algorithm for sampling the canonical distribution. In this approach the velocities of all the particles are rescaled by a properly chosen random factor. The algorithm is formally justified and it is shown that, in
spite of its stochastic nature, a quantity can still be defined that remains constant during the evolution. In numerical applications this quantity can be used to measure the accuracy of the sampling. We illustrate the properties of this new method on Lennard-Jones and TIP4P water models in the solid and liquid phases. Its performance is excellent and largely independent on the thermostat parameter also with regard to the dynamic properties.
