Configurational constant pressure molecular dynamics.

We propose two new algorithms for generating isothermal-isobaric molecular dynamics. The algorithms are based on an extended phase space dynamics where two extra degrees of freedom, representing the thermostat and the barostat, are included. These new methods adopt a totally different approach towards molecular dynamics simulation in the isothermal-isobaric ensemble. They are fully configurational in the sense that only the particle positions are required in the control of the system temperature and pressure. Following on from the works of Delhommelle and Evans [Mol. Phys., 99, 1825 (2001)] and of Braga and Travis [J. Chem. Phys., 123, 134101 (2005)] concerning configurational canonical dynamics, these new algorithms can be seen as a natural extension to the isothermal-isobaric ensemble. We have validated both of our new configurational isothermal-isobaric schemes by conducting molecular dynamics simulations of a Lennard-Jones fluid and comparing the static and dynamic properties for a single state point. We find that both schemes generate similar results compared with schemes which use kinetic temperature and pressure control. We have also monitored the response of the system to a series of isothermal compressions and isobaric quenches. We find that the configurational schemes performed at least as well as the kinetic based scheme in bringing the system temperature and pressure into line with the set point values of these variables. These new methods will potentially play a significant role in simulations where the calculation of the kinetic temperature and pressure can be problematic. A well known example resides in the field of nonequilibrium simulations where the kinetic temperature and pressure require a knowledge of the streaming velocity of the fluid in order to calculate the true peculiar velocities (or momenta) that enter into their definitions. These are completely avoided by using our configurational thermostats and barostats, since these are independent of momenta. By extending the analysis of Kusnezov et al. [Ann. Phys., 204, 155 (1990)] in order to derive a set of generalized Nose-Hoover equations of motion which can generate isothermal-isobaric dynamics in a number of different ways, we are able to show that both of our new configurational barostats and Hoover's kinetic isothermal-isobaric scheme are special cases of this more general set of equations. This generalization can be very powerful in generating constant pressure dynamics for a variety of systems.