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Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses
Published on: June 7, 2018
Temperature extrapolation of multicomponent grand canonical free energy landscapes
Nathan A Mahynski1, Jeffrey R Errington2, Vincent K Shen1
1Chemical Sciences Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-8320, USA.
Abstract:
We derive a method for extrapolating the grand canonical free energy landscape of a multicomponent fluid system from one temperature to another. Previously, we introduced this statistical mechanical framework for the case where kinetic energy contributions to the classical partition function were neglected for simplicity [N. A. Mahynski et al., J. Chem. Phys. 146, 074101 (2017)]. Here, we generalize the derivation to admit these contributions in order to explicitly illustrate the differences that result. Specifically, we show how factoring out kinetic energy effects a priori, in order to consider only the configurational partition function, leads to simpler mathematical expressions that tend to produce more accurate extrapolations than when these effects are included. We demonstrate this by comparing and contrasting these two approaches for the simple cases of an ideal gas and a non-ideal, square-well fluid.
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