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研究生:趙苑鳳
論文名稱:用理論計算的方法預測所有二價三價金屬離子在水溶液的pKa值
論文名稱(外文):pKa Prediction of Divalent and Trivalent Metal Hydrates:Linear Free Energy Relationship
指導教授:林小喬
指導教授(外文):Carmay Lim
學位類別:碩士
校院名稱:國立清華大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2003
畢業學年度:91
語文別:中文
論文頁數:45
中文關鍵詞:pK解離常數線性自由能二價金屬三價金屬
外文關鍵詞:pKionization constantlinear free energydivalent metalstrivalent metals
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  在此研究中 ,我們發展一套方法,藉著成功的預測相對的pKa值,進而得到所有二價三價金屬水合離子準確的絕對pKa值.此外,這套方法也可以幫助決定一些在生物上扮演很重要角色的金屬離子, 例如,Ca2+在水溶液中的CN,6-9實驗上都被發現,Zn2+ 在水溶液解離後, CN會從6變成5或4 ;藉由此套方法,我們可以決定Ca2+在水中主要的配位數 ,以及Zn2+水解後的配位數變化
   

We present a computational strategy to derive the absolute pK11 values of divalent and trivalent metal cations in aqueous solution from computed pK11 changes relative to the measured pK11 of a reference metal. We show that our strategy could yield accurate relative pK11 values, which, in turn, can help to determine key properties of biologically important metal cations in aqueous solution such as the dominant CN of Ca2+ and the CN of the deprotonated Zn2+ hexahydrate. The key factors governing the deprotonation of a metal-bound water molecule were identified.

Contents
1 Introduction 2
2 Methods 7
Systems Studied 7
PK11 Calculation 7
Geometry Optimization 8
Gas Phase Free Energy Calculations 9
Effective Solute Radii Optimization 12
3.Results And Discussions
Geometry Calibrations 13
Geometries of the Metal Hydrates 15
Geometries of the Deprotonated Metal Hydrates 18
Validating the Basis Set For Computing Gas Phase Deprotonation Energies 21
Correlation Between Geometrical Parameters and the Gas Phase Basicities 25
Effective Oxygen and Hydrogen Radii from Comparing Computed and
Experimental pK11 26
Testing the Computational Strategy by Predicting the pK11 values of Hg2+ , La3+
and Ga3+ 30
Verifying that Sc3+ , Y3+ and Cu2+ are not hexacoordinated 30
Predicting the dominating CN of Ca2+ 33
Predicting the Prederred CN of the deprotonated Zn2+ Complex 34
List of the Tables
Table 1. Effective Metal Radii from Experimental Hydration Free Energies (in kcal/mol) of Metal Cations. 11
Table 2. Calculated Average Metal-Oxygen (<M-O>) Distance±Standard Deviation (Å) in [M (H2O)n]2+/3+ Complexes Fully Optimized with Various Methods. 14
Table 3. Calculated Bond Distances (Å) and Angles (in degrees) in [M (H2O)n-1
(OH)]+/2+ Complexes Fully Optimized at the B3-LYP/ [SDD/6-31+G(d)] Level. 19
Table 4. Calculated Deprotonation Energies (DEe), Enthalpies (DHg), TDSg and Free Energies for [M (H2O)n]m+ ® [M (H2O)n-1 (OH)](m-1)+ + H+ (in kcal/mol). 24
Table 5. Comparison between Computed and Experimental DpK11 values of [M (H2O)n]2+/3+ Hydrates. 28
Table 6. Predicting the pK11 of Divalent and Trivalent Metal Hydrates 29

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