Determining the Crystal.pptVIP

Determining the Crystal-Melt Interfacial Free Energy via Molecular-Dynamics Simulation Brian B. Laird Department of Chemistry University of Kansas Lawrence, KS 66045, USA Ruslan L. Davidchack Department of Mathematics University of Leicester Leicester LE1 7RH, UK Funding: NSF, KCASC Observation #1 Not all important problems addressed with MD simulation are biological. Problem: Can one calculate the free energy of a crystal-melt interface using MD simulation? Crystal-melt interfacial free energy, gcl The work required to form a unit area of interface between a crystal and its own melt Why is the Interfacial Free Energy Important? ?cl is a primary controlling parameter governing the kinetics and morphology of crystal growth from the melt Why is the Interfacial Free Energy Important? ?cl is a primary controlling parameter governing the kinetics and morphology of crystal growth from the melt Why are simulations necessary here? Direct experimental determination of gcl is difficult and few measurements exist Indirect experimental measurement of gcl(Nucleation data and Turnbull’s rule) Calculating Free Energies via simulation:Why is Free Energy hard to measure? Unlike energy, entropy ( free Energy) is not the average of some mechanical variable, but is a function of the entire trajectory (or phase space) Free energy, F = E - TS, calculation generally require a series of simulations slowly transforming the system from a reference state to the state of interest Thermodynamic Integration Observation #2 In molecular simulation there are almost always two (or more) very different methods for calculating any given quantity Fluctuation Method Method due to Hoyt, Asta Karma, PRL 86 5530, (2000) h(x) = height of an interface in a quasi two-dimensional slab If q = angle between the average interface normal and its instantaneous value, then the stiffness of the interface can be defined The stiffness can be found from the fluctuations in