Simulating Vapor–Liquid Equilibria of PH 3 , AsH 3 , and SbH 3 from First Principles
Simulating Vapor–Liquid Equilibria of PH 3 , AsH 3 , and SbH 3 from First Principles
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从第一原理模拟 PH 3 、AsH 3 和 SbH 3 的汽液平衡
DOI：
10.1021/acs.jpcc.0c11495
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Siepmann, J. Ilja
中科院分区：
文献类型：
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作者：
Chen, Jingyi L.;Siepmann, J. Ilja
由于 V 族氢化物、磷化氢、胂和锑化氢的毒性、易燃性和化学不稳定性，其气液平衡尚未得到充分研究。使用 Kohn-Sham 密度泛函理论和两种流行的广义梯度近似泛函来描述分子间和分子内相互作用，进行吉布斯系综蒙特卡罗模拟，以获得 PH3、AsH3 和 SbH3 的气液共存曲线 (VLCC)。结合 Grimme、Goedecker-Teter-Hutter 赝势和双 ze 价极化基组的第三代色散校正，Perdew-Burke-Ernzerhof (PBE) 和 Becke-Lee-Yang-Parr (BLYP) 交换相关函数分别产生 PH3 的临界温度为 342 ± 8 和 289 ± 12 K，过度预测/低估实验值约 20 和 35 K。第一原理模拟的高计算成本需要相对较小的系统规模和较短的模拟，这可能会导致接近临界点的问题。对于 VLCC 和 PH3 的液体结构，没有观察到显着的系统尺寸影响。对于 AsH3 和 SbH3，PBE 交换相关函数预测的临界温度接近 450 K，该值比 AsH3 的现有文献值高出约 20%。
Because of their toxicity, flammability, and chemical instability, the vapor–liquid equilibria of the group V hydrides, phosphine, arsine, and stibine are underexplored. Gibbs ensemble Monte Carlo simulations were performed to obtain the vapor–liquid coexistence curves (VLCCs) for PH3, AsH3, and SbH3by using Kohn–Sham density functional theory with two popular generalized gradient approximation functionals to describe the inter- and intramolecular interactions. In conjunction with the third-generation dispersion correction of Grimme, Goedecker–Teter–Hutter pseudopotentials, and double-ζ valence polarization basis sets, the Perdew–Burke–Ernzerhof (PBE) and Becke–Lee–Yang–Parr (BLYP) exchange-correlation functionals yield critical temperatures for PH3of 342 ± 8 and 289 ± 12 K, respectively, that overpredict/underpredict the experimental value by about 20 and 35 K. The high computational cost of first-principles simulations necessitates relatively small system sizes and short simulations that can lead to problems near the critical point. No significant system size effects were observed for the VLCC and liquid structure of PH3. For AsH3and SbH3, the predicted critical temperatures with the PBE exchange-correlation functional are close to 450 K, a value about 20% above the available literature value for AsH3.