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| Title: | 鋅、鎳、鉻、鐵中心金屬紫質染料的相對能階比較 |
| Other Titles: | Relative orbital energy level comparison of zinc(II), nickel(II), chromium(II) and iron(II) porphyrin sensitized dye |
| Authors: | 莊文華;Chuang, Wen-hua |
| Contributors: | 淡江大學化學學系碩士班
王伯昌;Wang, Bo-cheng |
| Keywords: | 染料敏化太陽能電池;B3LYP;紫質;Dye-Sensitized Solar Cell;B3LYP;porphyrin. |
| Date: | 2009 |
| Issue Date: | 2010-01-11 02:42:27 (UTC+8) |
| Abstract: | 本研究之中所比較的中心金屬分別為鋅、鎳、鉻與鐵皆為全填滿組態(closed-shell)，且都在文獻上找到具備四方平面(Square planar)之四配位結構的晶體資料數據，因此可以利用此可能形成的結構加以討論計算與相互比較，達到化學分子尚未合成之前能夠加以評估之目的。在此我們運用B3LYP計算方法比較異核中心金屬紫質環狀分子結構，從其能階等計算數據相互比較，期望能從其中找出一些規則，並將其應用於染料敏化太陽能電池(Dye-sensitized Solar Cell, DSSC)之合成設計評估，快速的得到初步評估的有效方向。
計算結果指出，在相同的中心金屬比較，其能階大小順序為MTPLA系列<MTPB系列<MTPP系列，其中MTPLA含有氰基官能基，MTPB則是苯甲酸基，MTPP則為沒有取代基的型式，得知藉由LUMO接受者以氰基官能基取代，可以有效地降低其LUMO的能階，而且其HOMO下降值較LUMO小，造成MTPLA系列的能隙較低，而電子從HOMO躍遷至LUMO時所損耗的能量較少。
進一步從電子密度的分佈來探討其HOMO與LUMO的情形，MTPLA系列的有機金屬錯合物，因為氰基官能基在LUMO接受者所造成的影響，使得HOMO躍遷至LUMO能階時，電子密度大部份皆往羧基官能基的方向轉移，此種轉移有利於電子的傳導。
In this study, the metal ions in the central of major compound respectively are zinc (II), nickel (II), chromium (II) and iron (II) with close shell configurations, and all of these can all be found out the crystal data of four coordinations structure of having square planar data on the cultural heritage. Therefore, we can make use of this structure that may be formed to discuss, calculate and compare mutually, and that can achieve the purpose of evaluating before the chemistry molecule hasn’t been synthesized. We take advantage of the B3LYP calculation to mutually compare, expecting to find out some rules among them, and apply it to design an assessment at the synthesis of dye sensitizing solar cell, quickly get the effective direction of initial assessment.
The computation results pointed out that among the comparison of the same central metal, the step size order of its energy gap are MTPLA series < MTPB series < MTPP series. MTPLA includes the cyano function group, and MTPB includes the benzoic acid group, but MTPP is without the substituting group. It revealed that the LUMO receptor by cyano function group can reduce its LUMO effectively. Moreover, its HOMO drop value compared to LUMO’s is smaller, causing the energy gap of the MTPLA series to be lower. The electrons from the HOMO to LUMO lose less energy.
Furthermore, the distributions of electron density were discussed, especially in the HOMO and LUMO states. The MTPLA series with cyano function group have high electron density near the carboxyl group in the LUMO state. When the electrons transition arise from HOMO to LUMO, the electron density shift from central metal to carboxyl group. This kind of transfer would be beneficial for developments of dye sensitizing solar cell. |
| Appears in Collections: | [Graduate Institute & Department of Chemistry] Thesis
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