Anisotropic pressure molecular dynamics for atomic fluid systems

The MTK equations (Martyna G J, Tobias D J and Klein M L 1994 J. Chem. Phys. 101 4177-89), which simulate the constant-pressure, constant-temperature NPT ensemble, have been modified to simulate an anisotropic pressure along a single coordinate axis, thus rendering the NP_zzT ensemble. The necessary theory of non-Hamiltonian systems is briefly reviewed in order to analytically prove that the proposed equations indeed sample the desired ensemble. A previously derived geometric integrator for the MTK equations is modified to take into account the anisotropic pressure and volume fluctuations. We choose a Lennard-Jones fluid as an illustrative example. The density distribution function, as well as various thermodynamic and interfacial properties of the model system in a liquid-vapour coexistence state, was computed to test the robustness of the proposed equations of motion to simulate the NP_zzT ensemble.