Calculation of thermodynamic properties of Ni nanoclusters via selected equations of state based on molecular dynamics simulations

We present an approach for constant-pressure molecular dynamics simulations. This approach is especially designed for finite systems, for which no periodic boundary condition applies. A molecular dynamics (MD) simulation for Ni nanoclusters is used to calculate their pressure–volume–temperature (p–v–T) data for the temperature range 200 K≤T≤400 K, and pressures up to 600 kbar. Isothermal sets of p–v–T data were generated by the simulation; each set was fitted by three equations of state (EoSs): Linear Isotherm Regularity-II (LIRII), Birch–Murnaghan (BM), and EOS III. It is found that the MD data are satisfactorily reproduced by the EoSs with reasonable precision. Some features of the EoSs criteria, such as the temperature dependences of the coefficients, the isothermal bulk modulus and its pressure derivative at the zero-pressure limit, and isobaric thermal expansion for Ni nanoclusters, are investigated. We have found that same EoSs are valid for both bulk Ni and Ni nanoclusters, but with different values of the parameters, which depend on the cluster size and temperature. An increase in bulk modulus with decrease of cluster size can be observed. Also, an increase in isobaric expansion coefficient with decrease of cluster size has been found.

► We present an approach for constant-pressure molecular dynamics simulations.
► Isothermal sets of p–v–T data generated by the simulation were each fitted by three EoSs.
► An increase in bulk modulus with decrease of cluster size can be observed.
► An increase in isobaric expansion coefficient with decrease of cluster size has been found.