Theoretical Study of the Monohydration of Mercury Compounds of Atmospheric Interest
Theoretical Study of the Monohydration of Mercury Compounds of Atmospheric Interest
复制标题
大气汞化合物一水合的理论研究
DOI：
10.1021/acs.jpca.1c02772
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Louis, Florent
中科院分区：
文献类型：
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作者：
Taamalli, Sonia;Pitoňák, Michal;Dibble, Theodore S.;Černušák, Ivan;Louis, Florent
使用 ωB97X-D/aug-cc-pVTZ 理论水平对含氧汞化合物一水合物（BrHgO、BrHgOH、BrHgOOH、BrHgNO2、BrHgONO 和 HgOH）的结构、振动频率和模型红外光谱进行了理论研究。基态势能表面表现出这些一水合物的几种稳定结构。水合反应的热力学性质已在不同的理论水平上进行了计算，包括 DFT 和使用 ANO-RCC-Large 基组的耦合簇计算 DK-CCSD(T)。计算了水合的标准焓和吉布斯自由能。评估了 200–400 K 温度范围内最稳定配合物的 ΔrG°(T) 的温度依赖性。热力学数据显示，在 298 K 和 100% 相对湿度下水合的最高部分将是约 5% 的 BrHgNO2–H2O。
The structures, vibrational frequencies, and model IR spectra of the monohydrates of oxygenated mercury compounds (BrHgO, BrHgOH, BrHgOOH, BrHgNO2, BrHgONO, and HgOH) have been theoretically studied using the ωB97X-D/aug-cc-pVTZ level of theory. The ground state potential energy surface exhibits several stable structures of these monohydrates. The thermodynamic properties of the hydration reactions have been calculated at different levels of theory including DFT and coupled-cluster calculations DK-CCSD(T) with the ANO-RCC-Large basis sets. Standard enthalpies and Gibbs free energies of hydration were computed. The temperature dependence of ΔrG°(T) was evaluated for the most stable complexes over the temperature range 200–400 K. Thermodynamic data revealed that the highest fraction hydrated at 298 K and 100% relative humidity will be BrHgNO2–H2O at ∼5%.