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標題: | 開發嚴謹與可靠的方法用於預測柔性分子之熱力學性質 A Rigorous and Robust Approach for Thermodynamic Properties Prediction of Flexible Molecules |
作者: | Yi-An Chen 陳奕安 |
指導教授: | 林祥泰(Shiang-Tai Lin) 林祥泰(Shiang-Tai Lin | stlin@ntu.edu.tw | ), |
關鍵字: | 分子構型,構型異構物,狀態方程式,蒸氣壓,正辛醇—水分配係數, molecular conformation,conformer,equation of state,PR+COSMOSAC,vapor pressure,1-octanol-water partition coefficient, |
出版年 : | 2022 |
學位: | 碩士 |
摘要: | 分子的熱力學性質是化學工業中不可或缺的資訊,尤其在程序設計時,熱力學性質的預測是至關重要的。目前已有許多研究指出,分子的構型也是影響分子熱力學性質的重要因素之一,但在常用的熱力學模型中通常只考慮分子的單一一個構型做為代表,因而限制了模型的準確性。在此研究中,我們結合熱力學中的化學反應平衡與溶合計算,嚴謹地推導出能快速計算在液相中不同構型比例且自洽 (self-consistent) 的公式。透過PR+COSMOSAC 狀態方程式,輔以此研究中提出的構型異構物比例計算公式,使得 PR+COSMOSAC 狀態方程式在考慮構型的影響下,能夠得到更準確的蒸氣壓與正辛醇—水分配係數。此研究也提出將構型納入熱力學性質預測的自動化標準程序,藉由分析大量的計算結果,提出從構型搜索、量子化學計算、熱力學性質預測的完整可靠的自動化流程。最後也使用此研究提出的標準計算流程,計算超過一千個分子在不同構型影響下的蒸氣壓與正辛醇—水分配係數,並分析構型對分子熱力學性質的影響。 The conformation of a molecule is important information in chemical engineering, especially for the process design. The conformation of a molecule also significantly affects the thermodynamic properties of a chemical species. However, most of the common thermodynamic models used to predict the properties either have no capability to consider the conformational effect or only consider one conformation as the representation of the molecule. The ignorance of the conformational effect of these models limits the performance of the thermodynamic property predictions, especially for systems containing flexible molecules. In this work, combining the chemical reaction calculations and solvation calculations, we rigorously derived a self-consistent equation for rapid conformer distribution prediction. By the PR+COSMOSAC equation of state and the proposed conformer distribution equation, we could improve the AARD of PR+COSMOSAC EOS in vapor pressure prediction by about 20% compared to typical approaches. Furthermore, we also proposed a standard, automated calculation procedure for thermodynamic property predictions with the consideration of molecular conformations. Our proposed procedure handles the conformer search, quantum calculation, and thermodynamic prediction automatically and robustly. With our proposed calculation procedure, we tested the performance of vapor pressure and 1-octanol-water partition coefficient for more than a thousand molecules and analyzed how the conformations of a molecule could affect the predicted thermodynamic properties. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/86483 |
DOI: | 10.6342/NTU202202373 |
全文授權: | 同意授權(全球公開) |
電子全文公開日期: | 2023-09-01 |
顯示於系所單位: | 化學工程學系 |
文件中的檔案:
檔案 | 大小 | 格式 | |
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U0001-1408202200542300.pdf | 2.68 MB | Adobe PDF | 檢視/開啟 |
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