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The free energy landscape responsible for crystallization can be complex evenfor relatively simple systems like hard sphere and charged stabilized colloids.In this work, using hard-core repulsive Yukawa model, which is known to showcomplex phase behavior consisting of fluid, FCC and BCC phases, we studied theinterplay between the free energy landscape and polymorph selection duringcrystallization. When the stability of the BCC phase with respect to the fluidphase is gradually increased by changing the temperature and pressure at afixed fluid-FCC stability, the final phase formed by crystallization is foundto undergo a switch from the FCC to the BCC phase, even though FCC remainsthermodynamically the most stable phase. We further show that the nature oflocal bond-orientational order parameter fluctuations in the metastable fluidphase as well as the composition of the critical cluster depend delicately onthe free energy landscape, and play a decisive role in the polymorph selectionduring crystallization.

Polymorph selection during crystallization of a model colloidal fluid with a free energy landscape containing a metastable solid