A fundamental link between conceptual density functional theory and statistical thermodynamics is herein drawn, showing that intermolecular electrostatic interactions can be understood in terms of effective work and heat exchange. From a more detailed analysis of the heat exchange in a perturbation theory framework, an associated entropy can be subsequently derived, which appears to be a suitable descriptor for the local polarisability of the electron density. A general rule of thumb is evidenced: the more the perturbation can be spread, both through space and among the excited states, the larger the heat exchange and entropy.

中文翻译：

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电子密度极化的统计热力学观点：在化学选择性中的应用

本文绘制了概念密度泛函理论与统计热力学之间的基本联系，表明可以通过有效功和热交换来理解分子间静电相互作用。通过在扰动理论框架中对热交换进行更详细的分析，可以得出相关的熵，这似乎是电子密度的局部极化率的合适描述子。有一条一般的经验法则：扰动在空间和激发态之间的传播越多，热交换和熵越大。