ONIOM 方法中的 DFT 方法和分散校正模型对钕基齐格勒-纳塔催化剂上丁二烯聚合活化能的影响

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL International Journal of Quantum Chemistry Pub Date : 2024-08-08 DOI:10.1002/qua.27462
Alexey N. Masliy, Ildar G. Akhmetov, Andrey M. Kuznetsov, Ilsiya M. Davletbaeva
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引用次数: 0

摘要

在本研究中,我们使用双层 ONIOM 方法模拟了丁二烯在钕基齐格勒-纳塔催化剂上聚合过程中聚合物链的起始和生长阶段。DFT 方法 B3LYP 和 PBE0 与 Def2-TZVP 原子基集相结合被用作 ONIOM 的高级方法。Grimme 的半经验 XTB1 方法被用作低级方法。我们在之前的工作中详细研究了丁二烯在含钕齐格勒-纳塔催化剂上的聚合机理。研究发现,61 kJ/mol 的聚合活化能略高于该参数的实验测定值。在本研究中,研究了考虑分散相互作用的高级方法和模型对聚合反应活化参数计算质量的影响。在齐格勒-纳塔催化剂存在下,二烯烃聚合反应的实验活化能在 30-60 kJ/mol 之间,但钕基催化剂的活化能更接近这一范围的下限。为了进行比较,我们使用了半经验 Grimme 模型 D3 和 D4。结果表明,在 B3LYP 方法中,这两个模型显示的活化能几乎相同,而在 PBE0 方法中,活化能下降到 41 kJ/mol。因此,在 ONIOM 方法中使用 PBE0 作为高级方法,并在 D4 模型中考虑弥散相互作用,可以得到与实验数据更为一致的结果。
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Effect of DFT Methods and Dispersion Correction Models in ONIOM Methodology on the Activation Energy of Butadiene Polymerization on a Neodymium-Based Ziegler–Natta Catalyst

In present work, using the double layer ONIOM methodology, we simulated the stages of initiation and growth of the polymer chain during the polymerization of butadiene on a neodymium-based Ziegler–Natta catalyst. The DFT methods B3LYP and PBE0 in combination with the Def2-TZVP atomic basis set were used as high-level methods in ONIOM. Grimme's semi-empirical XTB1 method was used as a low-level method. In our previous work, the mechanism of butadiene polymerization on a neodymium-containing Ziegler–Natta catalyst was studied in detail. The polymerization activation energy of 61 kJ/mol was found to be slightly higher than the experimentally determined values of this parameter. In the present work, the influence of a high-level method and a model of taking into account dispersion interactions on the quality of calculation of activation parameters of the polymerization reaction was studied. Experimental activation energy for the polymerization of dienes in the presence of Ziegler–Natta catalysts is in the range of 30–60 kJ/mol, but neodymium-based catalysts have an activation energy somewhat closer to the lower limit of this range. For comparison, semi-empirical Grimme models D3 and D4 were used. It has been established that the both models reveal within the B3LYP method the activation energy practically the same, while within the PBE0 method it decreases to 41 kJ/mol. Thus, using the PBE0 as a high-level method within the ONIOM methodology and taking into account dispersion interactions within the D4 model leads to results in much better agreement with experimental data.

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来源期刊
International Journal of Quantum Chemistry
International Journal of Quantum Chemistry 化学-数学跨学科应用
CiteScore
4.70
自引率
4.50%
发文量
185
审稿时长
2 months
期刊介绍: Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.
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