利用量子化學方法建立混合型分子二聚體分子間相互作用力資料庫與混合法的比較分析

Quantum Chemistry Calculated Intermolecular Interaction Database of Mixing Molecular Dimers and Comparison of Six Mixing Rules

黃星翔(Hsing-Hsiang Huang)

指導教授 ： 趙聖德

國立臺灣大學/工學院/應用力學研究所/碩士(2019年)

https://doi.org/10.6342/NTU201904072

摘要

第一部份是建立混合型分子二聚體的分子間作用力資料庫，非共價鍵的分子間作用力在超分子化學、材料科學和生物化學……等領域皆是研究的重點，過去數十年來量子化學迅速地推陳出新，修正了計算結果的精度，而最後計算結果仍然需要與實驗結果相比，但有些能量參數無法被簡易量測或架設實驗的條件太過嚴苛，所以利用量子化學計算結果經分類與整理建構精準且方便參數化與測試用途的資料庫。而過去實驗室建立過同分子二聚體的分子間作用力資料庫，為了完備這方面資料庫的內容，本研究以混合型二聚體(bimers)的分子間作用力做為我的計算對象，使用常見的量子化學軟體Gaussian09去找到bimer的幾何與作用力，且利用MP2與CCSD(T)這兩種波函數發展得來的計算方法搭配DZ~ATZ基底來找出最佳化後的幾何，另外利用外插法求取的完整基底極限值，比較兩者收斂性與精度。
第二部份在建立混合型二聚體分子間作用力後，發現Bimer較Dimer數量多出許多，想利用Dimer的平衡位置和能量去猜測或預估Bimer能量與平衡位置，將能大幅減少計算時間和資源，而過去的研究混合理論大多應用在原子的系統或類球型分子中，本研究利用波茲曼分布使分子能應用混合理論，在利用混合理論所作來的結果與量子化學做出的結果做比較，經整理找出最佳的混合理論。
第三部份建立混合型二聚體分子間作用力後，利用SAPT方法搭配ATZ基底把能量拆解成四個分量，如與吸引力有關的靜電、誘導、色散和與斥力有關的交換項等有物理意義的分量，確定作用力建構規則，想透過SAPT分析的結果去討論這四種分量是怎麼由團基建構出來的。將其命名為團基作用力，之後只要給團基的組成就能找出全部的作用力，並可用於預估大型bimer的作用力。

關鍵字

作用力資料庫 ； 耦合簇理論 ； 非共價鍵作用力 ； 分子間作用力 ； 混合理論 ； 團基作用力 ； 混合型分子二聚體 ； SAPT ； 微擾理論

並列摘要

The first section is establishing intermolecular database by quantum chemistry. Because intermolecular force is necessary in many fields. Over five decades, the new quantum chemistry methods and equipments that improve the result. In many cases, the result be determined by experimental ways cannot be directly got parameterized value. Thus, it is important to create a database. Its function is conveniently parameterized application and test. In the past research, someone established the database of dimers. The dimers which are common functional groups contain hydrocarbon (alkane, alkene, alkyne),weak hydrogen bond types(alcohol, aldehyde, ketone), strong hydrogen bond types (acid and amide). To complete this database, intermolecular energy of the bimers are our computing objects. The bimers means different molecular dimers (such as methane to ethane ). Using Gaussian09 to simulate the configuration of bimers and calculate intermolecular forces, we used MP2 way with Dunning’s basis sets. Besides, we also used coupled cluster ways (CCSD(T)) to calculate interaction energy. At last, we used Complete Basis Set limit to compare with each ab initio method result. we discussed CBS convergence in relationship with increasing basis set .
After established the database of bimers , we discovered the number of calculations of bimers is more than dimers. we would like to estimate the energy and position of bimers by using the energy and position of dimers. This will greatly reduce computing resources and time. The past research mixing rule is mostly used in atomic systems or spheroidal molecules. This research uses the Boltzmann distribution to apply molecular to mixing rule. The results obtained using the mixing rule are compared with the results of quantum chemistry and collated to find the best mixing rule.
The third part : After the database of bimers is constructed, we used SAPT method to dismantle the intermolecular interaction to some parts like exchange、induction、dispersion、electrostatic terms. We further analyze the repulsive force terms and attractive force terms of bimers. To get the construct of intermolecular energy, and we also want to realize the SAPT results to find the four terms are from which molecular segmental group interaction of bimers.

並列關鍵字

(MP2) perturbation theory ； Noncovalent interaction ； SAPT ； Mixing rule ； (CCSD(T))coupled cluster method ； molecular segmental group interaction ； Intermolecular interaction energy database

參考文獻

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