Nuclear quantum effects on the quasiparticle properties of the chloride anion aqueous solution within the GW approximation
Nuclear quantum effects on the quasiparticle properties of the chloride anion aqueous solution within the GW approximation
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DOI：
10.1103/physrevb.104.035117
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发表时间：
2021-07-08
影响因子：
3.7
通讯作者：
Wu, Xifan
中科院分区：
文献类型：
--
作者：
Tang, Fujie;Xu, Jianhang;Wu, Xifan
离子溶液中的光电子光谱实验揭示了重要的电子结构信息，其中可以推断出水合离子与水溶剂之间的相互作用。基于具有GW近似的多体扰动理论，我们从理论上计算了氯化阴离子溶液的准粒子电子结构，该结构是通过核量子效应（NQES）来通过途径综合分子动力学模拟来建模的。确定水合阴离子和水的电子水平与最近的实验光电子光谱进行了比较。发现NQE改善了理论预测与实验之间的一致性，因为NQE有效地削弱了Cl nion和水之间的杂交。我们的研究表明，NQE在预测Hofmeister系列离子水溶液的电子结构中起很小但不可忽略的作用。
Photoelectron spectroscopy experiments in ionic solutions reveal important electronic structure information, in which the interaction between hydrated ions and water solvent can be inferred. Based on many-body perturbation theory with GW approximation, we theoretically compute the quasiparticle electronic structure of chloride anion solution, which is modeled by path-integral ab initio molecular dynamics simulation by taking account the nuclear quantum effects (NQEs). The electronic levels of hydrated anion as well as water are determined and compared with the recent experimental photoelectron spectra. It is found that NQEs improve the agreement between theoretical prediction and experiment because NQEs effectively weaken the hybridization of the between the Cl- anion and water. Our study indicates that NQEs plays a small but non-negligible role in predicting the electronic structure of the aqueous solvation of ions of the Hofmeister series.