Pressure-assisted decomposition of tricresyl phosphate on amorphous FeO using hybrid quantum-classical simulations,Journal of Computational Chemistry

当前位置： X-MOL 学术 › J. Comput. Chem. › 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.)

Pressure-assisted decomposition of tricresyl phosphate on amorphous FeO using hybrid quantum-classical simulations
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2022-11-22 , DOI: 10.1002/jcc.27039
Sota Hayashi ₁ , Naoki Uemura ₂ , Masayuki Uranagase ₁ , Shuji Ogata ₁

Affiliation

The moving components of combustion engines are operated under harsh conditions of high pressures and temperatures. Extreme-pressure anti-wear additives, such as tricresyl phosphate (TCP), are mixed with base oil to prevent wear through the formation of a lubricant film on the substrate. We studied the effect of liquid pressure on the decomposition pathway of TCP in base oil molecules (2,5-dimethylhexane) using hybrid quantum-classical simulations with density functional theory for electrons. At a temperature of 300 K, we found that: (i) bond-breaking barrier energies of both the OC and PO bonds of TCP decrease monotonically as the liquid pressure increases; (ii) the bond-breaking barrier energy of PO is lower than that of OC at pressures of 0 and 2.0 GPa, but is higher at a pressure of 5.0 GPa; and (iii) the applied pressure significantly lowers the bond-breaking barrier energies of both OC and PO when the PO bond of TCP is directed upward from the substrate. These findings are explained by the inhomogeneous distribution of base oil molecules around TCP and the steric repulsion of the PO bond of TCP. These results indicate that the internal structures of the lubricant films are pressure-dependent.

中文翻译：

使用混合量子经典模拟在无定形 Fe3O 上压力辅助分解磷酸三甲苯酯

内燃机的运动部件在高压和高温的恶劣条件下运行。将磷酸三甲苯酯 (TCP) 等极压抗磨添加剂与基础油混合，通过在基材上形成润滑油膜来防止磨损。我们使用混合量子经典模拟和电子密度泛函理论研究了液体压力对基础油分子（2,5-二甲基己烷）中 TCP 分解途径的影响。在 300 K 的温度下，我们发现：（i）随着液体压力的增加，TCP 的 O  C 和 P  O 键的破键势垒能单调下降；(ii) P  O的断键势垒能低于 O C 在 0 和 2.0 GPa 的压力下，但在 5.0 GPa 的压力下更高；(iii)当 TCP 的 PO 键从基底向上时，施加的压力显着降低了 OC 和 PO 的破键势垒能。这些发现可以用 TCP 周围基础油分子的不均匀分布和 TCP 的 PO 键的空间排斥来解释。这些结果表明润滑膜的内部结构与压力有关。

更新日期：2022-11-22

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11