ABSTRACT In this work, we present a method to compute the Pauli repulsion contribution to the solute-solvent interaction that exploits solute electronic configurations sampled by Quantum Monte Carlo simulations. Starting from the inspiring model of Amovilli and Mennucci, the discreteness of the solvent is recovered by the definition of molecular domains and the concept of probe molecule. The method can be calibrated on the solute ground state but it offers the advantage of being able to be applied also to electronic-excited states. We show the results for the formaldehyde-water intermolecular pair, here used for the calibration, and two clusters containing acrolein surrounded by 11 and 19 water molecules simulating the solvation shell. In these systems, hydrogen bonds are formed between the solute and the water molecules and we found that, in such case, the Pauli repulsion contribution gives a red shift in the n → π* vertical transition energy.

中文翻译：

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溶质-溶剂泡利排斥对水溶液中丙烯醛的 n → π* 跃迁的影响

摘要 在这项工作中，我们提出了一种计算泡利排斥对溶质 - 溶剂相互作用的贡献的方法，该方法利用了量子蒙特卡罗模拟采样的溶质电子配置。从 Amovilli 和 Mennucci 的启发性模型出发，通过分子域的定义和探针分子的概念来恢复溶剂的离散性。该方法可以在溶质基态上进行校准，但它提供了也能够应用于电子激发态的优势。我们展示了甲醛-水分子间对的结果，这里用于校准，以及两个包含丙烯醛的簇，被 11 和 19 个水分子包围，模拟溶剂化壳。在这些系统中，溶质和水分子之间形成氢键，我们发现，