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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机译：我们推导了一种从一个温度到另一个温度外推多组分流体系统大正则自由能态的方法。以前，我们为简单起见忽略了对经典分配函数的动能贡献的情况，引入了这种统计力学框架。 A. Mahynski et al。，J.Chem。物理> 146 ，074101（2017年）]。在这里，我们概括了推导这些贡献的推导，以明确说明所产生的差异。具体来说，我们展示了如何先验地考虑动能影响，以便仅考虑构型分配函数，从而导致较简单的数学表达式，与包括这些影响时相比，往往会产生更准确的推断。我们通过比较和对比这两种方法来证明理想气体和非理想方阱流体的简单情况，从而证明了这一点。
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