从第一原理模拟PH 3，AsH 3和SbH 3的汽液平衡,The Journal of Physical Chemistry C

当前位置： X-MOL 学术 › J. Phys. Chem. C › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

从第一原理模拟PH ₃，AsH ₃和SbH _3的汽液平衡
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2021-03-03 , DOI: 10.1021/acs.jpcc.0c11495
Jingyi L. Chen ₁ , J. Ilja Siepmann _{1,

2}

Affiliation

由于它们的毒性，易燃性和化学稳定性，因此对V族氢化物，膦，砷化氢和锑化氢的汽-液平衡未进行充分的研究。通过使用Kohn-Sham密度泛函理论和两种流行的广义梯度逼近泛函来描述分子间和分子内，进行了Gibbs集合蒙特卡罗模拟以获得PH ₃，AsH ₃和SbH ₃的气液共存曲线（VLCC）。互动。结合Grimme，Goedecker-Teter-Hutter伪电势和双ζ价极化基集的第三代色散校正，Perdew-Burke-Ernzerhof（PBE）和Becke-Lee-Yang-Parr（BLYP）交换-相关函数产生PH的临界温度₃ 342±8 289±12 K，分别，即高估了/ underpredict实验值约20和35 K.第一原理仿真必要的高计算成本相对小的系统尺寸和短的模拟，可导致邻近的问题关键点。对于VLCC和PH _3的液体结构，未观察到明显的系统尺寸影响。对于AsH ₃和SbH ₃，具有PBE交换相关功能的预测临界温度接近450 K，比AsH ₃的现有文献值高约20％。

"点击查看英文标题和摘要"

Simulating Vapor–Liquid Equilibria of PH3, AsH3, and SbH3 from First Principles

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 SbH₃ by 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 PH₃ of 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 AsH₃ and 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.

更新日期：2021-03-11

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南