Controlling relative polymorph stability in soft porous crystals with a barostat.

Abstract

We use Monte Carlo simulations to investigate the thermodynamic behavior of soft porous crystal (SPC) adsorbents under the influence of an external barostat. We consider SPCs that naturally exhibit polymorphism between crystal forms of two distinct pore sizes. In the absence of barostatting, these crystals may be naturally divided into two categories depending on their response to stress applied by the adsorbate fluid: those which macroscopically deform and change the volume of their unit cell ("breathing") and those which instead undergo internal rearrangements that change the adsorbate-accessible volume without modifying the unit cell volume ("gate-opening"). When breathing SPCs have a constant external pressure applied, in addition to the thermodynamic pressure of the adsorbate fluid, we find that the free energy difference between the crystal polymorphs is shifted by a constant amount over the entire course of adsorption. Thus, their relative stability may be easily controlled by the barostat. However, when the crystal is held at a fixed overall pressure, changes to the relative stability of the polymorphs tend to be more complex. We demonstrate a thermodynamic analogy between breathing SPCs held at a fixed pressure and macroscopically rigid gate-opening ones which explains this behavior. Furthermore, we illustrate how this implies that external mechanical forces may be employed to tune the effective free energy profile of an empty SPC, which may open new avenues to engineer the thermodynamic properties of these polymorphic adsorbents, such as selectivity.