Isoenthalpic–isobaric ensemble

The isoenthalpic-isobaric ensemble (constant enthalpy and constant pressure ensemble) is a statistical mechanical ensemble that maintains constant enthalpy ${\displaystyle H\,}$ and constant pressure ${\displaystyle P\,}$ applied. It is also called the ${\displaystyle NPH}$-ensemble, where the number of particles ${\displaystyle N\,}$ is also kept as a constant. It was developed by physicist H. C. Andersen in 1980.[1] The ensemble adds another degree of freedom, which represents the variable volume ${\displaystyle V\,}$ of a system to which the coordinates of all particles are relative. The volume ${\displaystyle V\,}$ becomes a dynamical variable with potential energy and kinetic energy given by ${\displaystyle PV\,}$.[2] The enthalpy ${\displaystyle H=E+PV\,}$ is a conserved quantity.[3] Using isoenthalpic-isobaric ensemble of Lennard-Jones fluid, it was shown [4] that the Joule–Thomson coefficient and inversion curve can be computed directly from a single molecular dynamics simulation. A complete vapor-compression refrigeration cycle and a vapor–liquid coexistence curve, as well as a reasonable estimate of the supercritical point can be also simulated from this approach. NPH simulation can be carried out using GROMACS and LAMMPS.

References

1. Andersen, H. C. Journal of Chemical Physics 72, 2384-2393 (1980).
2. Hwee, Chiang Soo. "Mechanical behavior of peptides in living systems using molecular dynamics." Archived 2007-06-22 at the Wayback Machine
3. Other Statistical Ensembles
4. Kioupis, L. I.; Arya, G.; Maginn E. I. Pressure-enthalpy driven molecular dynamics for thermodynamic property calculation II: applications. Fluid Phase Equilibria 200, 93–110 (2002).