Solvent Induced Proton Polarization within the Nuclear−Electronic Orbital Framework
Solvent Induced Proton Polarization within the Nuclear−Electronic Orbital Framework
复制标题
核电子轨道框架内溶剂诱导质子极化
DOI：
10.1021/acs.jpclett.3c00471
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Li, Xiaosong
中科院分区：
文献类型：
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作者：
Lambros, Eleftherios;Link, Benjamin;Chow, Mathew;Hammes-Schiffer, Sharon;Li, Xiaosong
为了在化学过程的模拟中明确地考虑核量子效应和溶剂环境，核电子轨道方法与可极化连续模型（PCM）相结合。这NEO-PCM的方法是用来探索通过应用到水的二聚体和质子化水四聚体的溶剂化对核极化的影响。在这些物种的核极化分析质子密度和氧-氢键长度的变化。溶剂化被证明是提高核极化与增加介电常数。对于水二聚体，内部的氢键质子比外部的自由质子更容易被吸收。此外，质子量子化通过它们的相互极化导致更大的溶剂极化。这些计算突出了化学体系中电子、核和溶剂极化之间的复杂相互作用。
To explicitly account for nuclear quantum effects and solvent environments in simulations of chemical processes, the nuclear-electronic orbital approach is coupled with a polarizable continuum model (PCM). This NEO–PCM approach is used to explore the influence of solvation on nuclear polarization through applications to a water dimer and a set of protonated water tetramers. Nuclear polarization in these species is analyzed in terms of changes in proton density and oxygen–hydrogen bond length. Solvation is shown to enhance nuclear polarization with increasing dielectric constant. For the water dimer, the internal, hydrogen-bonded proton is shown to polarize more than the external, free proton. Moreover, proton quantization leads to greater solvent polarization through their mutual polarization. These calculations highlight the complex interplay among electronic, nuclear, and solvent polarization in chemical systems.