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利用Cluster－Continuum Solvation Model探...

國立高雄大學應用化學系碩士班

利用Cluster－Continuum Solvation Model探討Diels－Alder反應之溶劑效應 = Study Diels－Alder Reaction in Solution with Cluster－Continuum Solvation Model

Record Type:	Language materials, printed : monographic
Paralel Title:	Study Diels－Alder Reaction in Solution with Cluster－Continuum Solvation Model
Author:	張怡真,
Secondary Intellectual Responsibility:	國立高雄大學
Place of Publication:	[高雄市]
Published:	撰者;
Year of Publication:	[民99]2010
Description:	110面圖，表 : 30公分;
Subject:	溶劑模型
Subject:	solvation model
Online resource:	http://handle.ncl.edu.tw/11296/ndltd/69141775459388072318
Summary:	本論文主要利用混合密度泛函理論(Hybrid Density Functional Theory，簡稱HDFT)，配合三種溶劑模型(Cluster、Continuum及Cluster-Continuum Solvation Model)，計算甲基乙烯基酮(Methyl Vinyl Ketone，簡稱MVK)與環戊二烯(Cyclopetadiene，簡稱CP) Diels－Alder反應於氣相及不同溶劑中能量變化情形，以便了解反應受溶劑效應(Solvent effect)影響，而產生的活化能下降和反應速率常數提升之情形。計算發現，使用Cluster及Continuum Solvation Model兩種溶劑模型計算反應於氣相及水中活化自由能變化差值，和實驗值(△△G‡exp=3.85 kcal/mol)相比，有明顯低估的情形。反觀利用Cluster-Continuum Solvation Model計算反應活化自由能變化差值，與實驗相比僅差0.19 kcal/mol。另外，針對Cluster-continuum Solvation Model探討溶劑效應的部份，發現疏水效應(Hydrophobic effect)僅佔溶劑效應39.2%的影響力，大多數皆來自於疏水效應(Hydrogen bonding effect)之貢獻(60.8%)，與Explicit及Implicit solvation model結果相比即可發現，上述兩溶劑模型在計算疏水效應(75.6%)或氫鍵結效應(60.8%)對溶劑效應之影響力時，皆有高估之情形。經由分析數據後，此現象證實與Cluster及Continuum Solvation Model沒有考慮到近程(前者)及遠程(後者)作用力的干擾，降低疏水效應或氫鍵結效應對反應能量及速率變化的影響，因而產生計算誤差有關。 In this thesis, we investigated the activation energy of the Diels－Alder reaction in gas, aqueous, and in methanol solution. Free energy of Diels－Alder reaction of cyclopentadiene with methyl vinyl ketone have been computed using hybrid density functional theory(HDFT) and different solvation models. Compared to 3.85 kcal/mol which obtained by experimental rate constant difference between the gas and aqueous phase, the cluster and continuum solvation model both underestimate the activation free energies. However, the cluster-continuum solvation model gives the free energy difference were by 0.19 kcal / mol. Therefore, cluster-continuum solvation model is considered to be widely used to compute, analysis, and research chemical or physical property of reaction system in solvent. Results computed by cluster-continuum solvation model also showed that, most solvent effect caused from hydrogen bonding effect (60.8%), only 34% caused from hydrophobic effect. Therefore, computational results from explicit and implicit solvation model are considered to be overestimate (Hydrophobic effect：75.6%；Hydrogen bonding effect：60.8%). This consequence proved that using explicit and implicit solvation model to compute activation free energies of reaction change in different environment would cause errors by neglecting the interference of short-range (or long-range) interaction.

利用Cluster－Continuum Solvation Model探討Diels－Alder反應之溶劑效應 = Study Diels－Alder Reaction in Solution with Cluster－Continuum Solvation Model
張, 怡真

利用Cluster－Continuum Solvation Model探討Diels－Alder反應之溶劑效應 = Study Diels－Alder Reaction in Solution with Cluster－Continuum Solvation Model / 張怡真撰 - [高雄市] : 撰者, [民99]2010. - 110面 ; 圖，表 ; 30公分.
參考書目：面.
溶劑模型solvation model

利用Cluster－Continuum Solvation Model探討Diels－Alder反應之溶劑效應 = Study Diels－Alder Reaction in Solution with Cluster－Continuum Solvation Model
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330 $a 本論文主要利用混合密度泛函理論(Hybrid Density Functional Theory，簡稱HDFT)，配合三種溶劑模型(Cluster、Continuum及Cluster-Continuum Solvation Model)，計算甲基乙烯基酮(Methyl Vinyl Ketone，簡稱MVK)與環戊二烯(Cyclopetadiene，簡稱CP) Diels－Alder反應於氣相及不同溶劑中能量變化情形，以便了解反應受溶劑效應(Solvent effect)影響，而產生的活化能下降和反應速率常數提升之情形。計算發現，使用Cluster及Continuum Solvation Model兩種溶劑模型計算反應於氣相及水中活化自由能變化差值，和實驗值(△△G‡exp=3.85 kcal/mol)相比，有明顯低估的情形。反觀利用Cluster-Continuum Solvation Model計算反應活化自由能變化差值，與實驗相比僅差0.19 kcal/mol。另外，針對Cluster-continuum Solvation Model探討溶劑效應的部份，發現疏水效應(Hydrophobic effect)僅佔溶劑效應39.2%的影響力，大多數皆來自於疏水效應(Hydrogen bonding effect)之貢獻(60.8%)，與Explicit及Implicit solvation model結果相比即可發現，上述兩溶劑模型在計算疏水效應(75.6%)或氫鍵結效應(60.8%)對溶劑效應之影響力時，皆有高估之情形。經由分析數據後，此現象證實與Cluster及Continuum Solvation Model沒有考慮到近程(前者)及遠程(後者)作用力的干擾，降低疏水效應或氫鍵結效應對反應能量及速率變化的影響，因而產生計算誤差有關。 In this thesis, we investigated the activation energy of the Diels－Alder reaction in gas, aqueous, and in methanol solution. Free energy of Diels－Alder reaction of cyclopentadiene with methyl vinyl ketone have been computed using hybrid density functional theory(HDFT) and different solvation models. Compared to 3.85 kcal/mol which obtained by experimental rate constant difference between the gas and aqueous phase, the cluster and continuum solvation model both underestimate the activation free energies. However, the cluster-continuum solvation model gives the free energy difference were by 0.19 kcal / mol. Therefore, cluster-continuum solvation model is considered to be widely used to compute, analysis, and research chemical or physical property of reaction system in solvent. Results computed by cluster-continuum solvation model also showed that, most solvent effect caused from hydrogen bonding effect (60.8%), only 34% caused from hydrophobic effect. Therefore, computational results from explicit and implicit solvation model are considered to be overestimate (Hydrophobic effect：75.6%；Hydrogen bonding effect：60.8%). This consequence proved that using explicit and implicit solvation model to compute activation free energies of reaction change in different environment would cause errors by neglecting the interference of short-range (or long-range) interaction.
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