利用LCBO-MO理論方法中Weinhold的天然鍵結軌域計算，軌域作用的穩定能，E(2)值，來分析〝高分子與鋰離子所形成的錯合物〞以及〝鋰鹽分子內部〞電子不定域化情形。在高分子內尿素與乙醚兩單元，計算出氧孤立對電子對與鋰離子作用的E(2)值分別為15.4 kcal/mol、5.76 kcal/mol。發現此乃由於鋰離子的存在使得尿素內部電子不定化程度變大(約多出265 kcal/mol)，相反的，鋰離子配位於醚基的氧上，其內部電子不定域化程度反而會下降(22 kcal/mol)。因此，推論此鋰離子配位所產生的穩定能是鋰離子優先配位於尿素羰基氧上的原因。這樣的結果可以用來解釋文獻上聚醚基聚酉尿酯高分子鋰電池電解質的變溫7Li-NMR光譜分析。首先，隨著鋰離子濃度改變，鋰離子會先配位於尿素羰基的原上直到配位達飽和，鋰離子才會配位於醚基的氧上。其次，光譜中的兩個共振訊號分別為配位於高分子中尿素及乙醚的氧原子上Δδ = 0.70 ppm(計算Δδ = 0.54 ppm)，當鋰離子配位在胺基中酸氧上的訊號，計算得到的Δδ為0.10 ppm，因此會埋入鋰離子配位在羰基的訊號中，而無法看到。所以上述E(2)值分析以及計算出的相對化學位移值(Δδ)，可以解釋7Li NMR光譜。
　　下列鋰鹽導電度趨勢依序為: LiN(SO2CF3)2＞ LiCF3SO3＞LiClO4＞LiPF6＞LiBF4。由E(2)值之分析，發現LiPF6、LiBF4兩鋰鹽分別易分裂為(LiF＋PF5)以及(LiF＋BF3)，形成接近中性的分子。更進一步研究其他三鋰鹽，其相對導電度之趨勢可由此三鹽類的陰離子內部非定域化能量來解釋， E(2)值分別為2028 kcal/mol ( N(SO2CF3)2-)、985 kcal/mol
(CF3SO3-)、746 kcal/mol(ClO4-)。相對於CH3，CF3造成N(SO2CF3)2-、CF3SO3- 陰離子E(2)值分別增加452及158 kcal/mol，由此可看出含有CF3基的兩鋰鹽會因此拉電子基而使共振結構不定域化程度變大。此兩陰離子內的CF3基本身也有lp (F)→σ(C-F*) 非定化作用，其E(2)作用分別為 250及124 kcal/mol，此亦為含CF3基的鋰鹽具有較穩定的陰子，而呈現較高的導電度的原因。

　　Orbital interaction energies for Li+ in polyether(urethane urea) and for five lithium salts have been calculated by LCBO-MO method, in which the BOs were
constructed by the NBO method proposed by Weinhold. Analysis of values of E(2) indicates the stabilization of the lithium cation by the lone-paired electrons on oxygen
atom is greater in the urea unit (15.4 kcal/mol) than the ether unit (5.76 kcal/mol).The magnitudes of total E(2) within the urea system is enhanced by265 kcal/mol due
to the coordination of a lithium ion. On the other hand, the value of total E(2) is reduced from 152 to130 kcal/mol in ether unit by the lithium ion. The preference of
the urea oxygen, regarding to the coordination site, may be better explained by the considerable stabilization energy found for the lithium-coordinated system. The
conclusion drawn here can be employed to rationalize the reported 7Li-NMR recorded at various concentrations of the lithium ion. Firstly, the Li+ coordination on the ether
unit was not found unless at higher concentration at which the urea oxygen could not tolerate more lithium ions. Secondly, the two major resonance signals obtained by
two-component convolution were found with ∆δ=0.70 ppm, which is in good agreement with the calculated value, 0.54 ppm, in the present study. The third peak arising from the coordinated oxygen of carbamic acid was buried in the signal of the urea oxygen, since the calculated value of ∆δ is 0.10 ppm.
　　The published trend of conductivity for the five lithium salts under this study is:LiN(SO2CF3)2＞ LiCF3SO3＞LiClO4＞LiPF6＞LiBF4. The two least conductive salts are both calculated as two near neutral molecules, (LiF + PF5) and (LiF + BF3),respectively. This might explain their poor conductivities. Further investigation of
orbital interactions for the other three salts reveals that the relative conductivity can be explained by delocalization energies within the anions: 2028 kcal/mol
(N(SO2CF3)2-), 985 kcal/mo(CF3SO3-) and 746 kcal/mol(ClO4
-). Moreover, we perform the same studies on CH3-replacement analogues: LiN(SO2CH3)2 and LiCF3SO3 .It is found that CF3 group results in an increased delocalization
energies452 and158 kcal/mol , respectively. It is also informative that the CF3 group itself also provides, respectively,250and124 kcal/mol of delocalization energy. One can conclude that the CF3 group would stabilize the counter ion of Li+ by two mechanisms: the σ-withdrawing capability and the π-type orbital interactions, in
which lone-paired electron(s) delocalized to the CF σ-antibonding orbitals.

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