本研究第一次確立 DFT/B3LYP 計算對現今染料太陽能電池 (DSSCs)研究領域，包括含苯基的共軛化合物 (phenyl conjuration compounds) 、香豆素衍生物 (coumarin derivatives) 與三苯胺衍生物 (triphenylamine derivatives) 染料分子，是可以提供可靠的物理量。其中的三苯胺衍生物除了 HOMOs 能量較高的缺點之外，是具有潛力並且熱門的染料分子。經由利用化學取代以調整 π-type molecular orbitals (MOs) 之研究，傳統概念中氟的拉電子 (electron-withdrawing) 特性是不足以描述利用氟取代以穩定 π-type MOs 能量失敗的結果。另外，三氟甲基接受 π-type MOs電子 (π-accepting) 之特性，則是依照它的電負度而所預期得到的效果，卻不管其負超共軛 (negative hyperconjugation, NHC) 論點中已確立的 π-accepting 之性質。在此，將利用這兩種取代基來調整以三苯胺結構為基礎的染料分子其 HOMO/LUMO 能量。
MO 能量變化是由於取代基位置的不同所造成，有此可證氟也具有不穩定 MO 的效應 (MO-destabilization effects) 。當氟所在的碳，其對 MO 的貢獻越高時，就會就會造成 MO 能量下降的比較，或是較高的 MO 能量。而對於 HOMO 的影響是來的比 LUMO 還要顯著，這是因為 HOMO 能量上是比較接近氟的價殼層 p orbital，即 2p(F) 。而 p orbital 的推升 HOMO/LUMO 之效應可以利用 LCBO-MO 分析進行解釋，其分析則利用 Weinhold 的 NBO 方法對 DFT 波函數進行鍵結軌域 (bond orbital) 或是定域化 MOs (localized MOs) 分析可獲得。當氟化後，其氟的一中心鍵結軌域 2p(F) 有較高之貢獻值時，就會造成較高的 HOMO 或是 LUMO 軌域能量。這種 2p(F) 與 HOMO/LUMO 之間的交互作用造成的能量抬升，可視為 MO 的變化是伴隨著廣為人知的中介效應 (mesomeric effect，也稱作共振或是共軛效應)所造成的影響。
此外，三氟甲基的反鍵結 CF bond，即 *CF ，也會參與衍生物 HOMO/LUMO 的混成。 *CF 扮演 π-accepting 造成 HOMO/LUMO 能量的下降，這和 NHC 論點是一樣的，並且會與 2p(F) 所造成的推升效果相互抵消。上述經由 pi-framework 影響 MO 能量的雙重特性，是可以解釋用三氟甲基調整磷光顏色文獻中所提出 “純粹誘導效應” 之結論。還有，立體效應效應會造成異常於上述電子效應的 MOs 能量上升，這與實驗室另一項調整 Ir(III) 錯合物螢光能量之研究，是不謀而合的。

The DFT/B3LYP calculations have first been confirmed to provide reliable physical quantities published recently in the area of DSSC studies. The triphenylamine derivatives are promising and popular dyes except their high-lying HOMOs. Through the studies of adjusting the energies of pi-type molecular orbitals using chemical substitution, the conventional electron-withdrawing nature of fluoro suffers poor to failure results in view of lowering pi-type MOs. Conversely, the pi-accepting nature of a trifluoromethyl group gives results complying with expected effects based on its EN values despite of its pi-accepting nature well established by the negative hyperconjugation argument. The two substituents have been adapted for modifying the levels of HOMO/LUMO of the Triphenylamine-based dyes.
The MO-destabilization effects exerted by a fluoro have been verified through the site-dependent observation of MO-energy variations. As it is introduced at a carbon having more contribution to the MO wavefunction, the lowering extent gets smaller or would even lead to a higher MO energy. This is more pronounced for HOMO than for LUMO since the former is closer in energy to the valence p-orbital of fluorine, 2p(F). The pushing-up effect of p-orbital on HOMO/LUMO can be explained by analysis of LCBO-MO, in which the bond orbitals or localized MOs are extracted from the DFT wavefunctions by the Weinhold’s NBO method. Fluorination performed at a carbon having higher value of the one-center BO, 2p(F), results in a higher MO-energy of HOMO or LUMO. This destabilization described by the orbital interaction between 2p(F) and HOMO/LUMO can be viewed as the MO-variations accompanied by the well known mesomeric (also termed as resonance or conjugation) effect.
In addition to the CF anti-bonding, *CF, the 2p(F) BO of a trifluoromethyl group also contributes to HOMO/LUMO of the derivatives. The pi-accepting role played by *CF, which would press down HOMO/LUMO according to NHC argument, is offset by the 2p(F) destabilization effect. This dual nature, which affects MO-energies via pi-framework, explains the reported “purely inductive effect” found for color-tuning using trifluoromethyl group. As well as we have found for tuning phosphorescent energies of Ir(III) complexes, the steric effect would operate as the exceptional destabilization of MOs is found based on the above-stated electronic effects.

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