臺灣博碩士論文加值系統

我們利用量子化學計算的方法計算類胡蘿蔔素分子的生成焓(Hf)，我們研究的分子從最小單位的聚合烯類到含有九個雙鍵的聚合物分子，以及幾種的C40H56類胡蘿蔔素，其中所研究的類胡蘿蔔素包括了：-carotene、-carotene、lycopene以及prolycopene，在比較短的聚合物分子上，我們利用了G2、G3以及G3MP2理論，並且利用了atomization、isodesmic鍵分離以及homodesmic方法，在計算上面還外加了六個密度泛函理論(DFT)於計算中，並且將計算的數值與G3的atomization反應所計算出來的數值加以比較，為了能夠更接近G3的原子化法的數值，我們利用DFT與半經驗的理論經由atom equivalents以及 group equivalent的方法，我們可以發現到group equivalent搭配isodesmic反應是在所有的反應當中較為接近G3的數值，並且當中的六種DFT理論在這種方式上面也是相當接近的，在這些理論當中，B3LYP的理論算出來的數值與G3的參考數值較為接近，當中的平均絕對誤差僅僅只有0.30 kcal/mol，這也表示若是要用DFT的方法來求C40H56的Hf，是相當具有準確性的

Theoretical study of the enthalpies of formation (Hf) for polyenes up to nine ethylene units and for several C40H56 carotenes including -carotene, -carotene, lycopene, and prolycopene is presented. For polyenes and small branched alkenes we used G2, G3 and G3MP2B3 theories, and the Hf were evaluated with the atomization, isodesmic bond separation, and homodesmic schemes. The applicability of six DFT functionals were examined by comparing their predictions with those obtained using G3 theory within the atomization scheme. Additivity approaches, including atom equivalents and group equivalents using DFT and semiempirical theories were explored. We found that group equivalents associated with isodesmic reactions is able to provide most accurate predictions within the test set. The predictions from the six functionals are in good agreement with the G3 results. And among them B3LYP performs the best, with an average absolute deviation of only 0.30 kcal/mol. The application of DFT in the prediction for the Hf of C40H56 carotenes is promising.

Table 目錄 ii
Figure 目錄 iii

前言 1
第一章 緒論 4

第二章 理論計算方法 9

第三章 問題與討論 12
3.1小型分子 12
3.2聚合烯類 13
3.3原子當量數法與群當量數法的運用 17
3.4半經驗與參數法 20

第四章 結論 22

參考文獻 23

Table 目 錄
Table 1 小分子經由高階理論的原子化法計算所求得的Hf 28
Table 2 利用atomization isodesmic與homodesmic方法求得的Hf 29
Table 3 利用DFT理論在atomizatio與isodemic所求得的 Hf 30
Table 3-1利用DFT理論在homodesmic所求得的 Hf 31
Table 4 利用DFT在AE的方式下所測得的 Hf 32
Table 5利用DFT在GE的方式下所測得的 Hf 33
Table 6 C40H56在不同的DFT理論中利用GE的方式所求的 Hf 34
Table 7-1 用半經驗法AM1以及PM3的理論計算所得的Hf 35
Table 7-2用半經驗法所求具有支鏈分子的 Hf 36
Table 8在不同的理論以及半經驗法利用AE以及GE的參數法所求得Hf 37

Figure 目 錄
Figure 1 All-trans 與cis 形式的lycopene 25
Figure 2 聚合烯類(Pn，n=1-9)與類胡蘿蔔素C40H56的分子結構 26
Figure 3 具有支鏈分子的空間結構 27
Figure 4聚合物烯類的空間結構 38
Figure 5具有支鏈分子的空間結構 42
Figure 6類胡蘿蔔素分子C40H56的空間結構圖 44

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