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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >DFT study on isomerization and decomposition of cuprous dialkyldithiophosphate and its reaction with alkylperoxy radical
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DFT study on isomerization and decomposition of cuprous dialkyldithiophosphate and its reaction with alkylperoxy radical

机译：DFT研究二烷基二硫代磷酸亚铜的异构化和分解及其与烷基过氧自由基的反应

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摘要

The cuprous dialkyldithiophosphate [(RO)(2)PS2Cu, CuDDP] as an antioxidant has been industrially used in lubricating oil. In this paper, for the first time, a computational study has been carried out for CuDDP. The scaled hypersphere search method has been used to explore the isomerization and decomposition pathways of (HO)(2)PS2Cu, a model compound of CuDDP, and its reaction with CH3OO center dot radical. The calculations were performed at the B3LYP level of theory. The results show that the most stable structure of (HO)(2)PS2Cu has pseudo-C-2 nu, symmetry and a four-membered ring constructed by P, Cu, and two S atoms. The bondrearrangement isomerization leading to a (H)O-bridging structure is kinetically feasible. Three dissociation channels have been found for (HO)(2)PS2Cu, which require high energy (> 60 kcal/mol) under the investigated condition. The reaction of (HO)(2)PS2Cu with CH3OO center dot includes bond-rearrangement isomerization and the decomposition of CH3OO center dot moiety. The (HO)(2)PS2Cu-assisted CH3OO center dot decomposition occurs via its O-O bond cleavage or the C-O bond dissociation. The former decomposition manner has been computed to be preferable over the latter at low temperature, but calculations suggested for the latter decomposition manner at higher temperature. Such a decomposition reaction, which is endothermic but possible, may be related to the antioxidation process of CuDDP.
机译：作为抗氧化剂的二烷基二硫代磷酸亚铜[（RO）（2）PS2Cu，CuDDP]已在工业上用于润滑油中。本文首次对CuDDP进行了计算研究。规模化的超球搜索方法已用于探索（HO）（2）PS2Cu（CuDDP的模型化合物）的异构化和分解途径，以及其与CH3OO中心点自由基的反应。计算是在B3LYP的理论水平上进行的。结果表明，（HO）（2）PS2Cu的最稳定结构具有拟C-2 nu，对称性和由P，Cu和两个S原子构成的四元环。导致（H）O-桥接结构的键重排异构化在动力学上是可行的。已发现（HO）（2）PS2Cu的三个解离通道，在研究条件下需要高能量（> 60 kcal / mol）。 （HO）（2）PS2Cu与CH3OO中心点的反应包括键重排异构化和CH3OO中心点部分的分解。 （HO）（2）PS2Cu辅助的CH3OO中心点分解是通过其O-O键断裂或C-O键解离而发生的。已经计算出前者的分解方式在低温下比后者更好，但是计算结果建议了后者在高温下的分解方式。这种分解反应是吸热的，但可能发生，可能与CuDDP的抗氧化过程有关。

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