• 作者： 黃良平
• 作者服務機構： 國立台灣大學化學系及中央研究院分子研究所
• 中文摘要： (方程式無法摘錄) 在溶液中，電子自旋弛緩經理論計算顯示在低磁傷下，弛緩振盪衰減，因無ESR訊號，其電子自旋磁行為可經由核磁共振弛緩來評量在配位基上甲基之氫核，在8KG以下由自旋一晶格弛緩率分析得知，電子自旋的影響不能忽視，但在較高磁場貝1l須考慮電子一氫核間的偶極作用，因此磁作用的調制造成之核弛緩可研究 (方程式無法摘錄) 錯合分子之旋轉運動，結果顯示因外圍錯合物形成導致偏離卜朗運動型式。外圍錯合物之形成可藉氯仿氫核在四氯化碳混合溶液中之核弛緩率分析，求得外圍錯合物形成之穩定常數，再經由 (方程式無法摘錄) 代替 (方程式無法摘錄) 在（氘）氯仿取代之相對應系統求得氯仿和 (方程式無法摘錄) 2:1之結合數，結合之氯仿和配位基之三個氧原子形成三足鼎立的氫鍵，此現象亦經由重氫偶合 (方程式無法摘錄) 光譜線寬化差量得以證實。
• 英文摘要： ESR relaxations of (方程式無法摘錄) in a dilute solution are calculated from the stochastic Liouville equa-tion on the basis of eigenfunction expansion. Damping oscillation in relaxation decay is observed at lowfield and in the slow motion region. This shows the importance of the high order effect of zero-field-splitting interaction. The effects are confirmed from the frequency dependent study of the methyl protonspin-lattice rates of the complex below 35 MHz in chloroform solutions. The study also allows one toobtain the overall reorintational correlation times of the complex. However they show significant deviationfrom those predicted for simple brownian motion. The deviation was believed to be attributable to theeffects of outer-sphere-complex formation (OSC) between chloroform and (方程式無法摘錄) . The data on spin-lattice relaxation rates of the (方程式無法摘錄) proton in mixture solutions of (方程式無法摘錄) were used to evaluate thestability constant of the OSC. Then, a solvation number of two was determined from deuteron relaxationsin (方程式無法摘錄) solutions of (方程式無法摘錄) which is used as a diamagnetic correspondence of (方程式無法摘錄) . Thedistance between the paramagnetic center and chloroform molecule is also calculated. The result is con-firmation that the solvation of the complex is due to the formation of a trifurcated hydrogen bond betweenchloroform and (方程式無法摘錄) . The differential line brodening effects of (方程式無法摘錄) on deuteron-split (方程式無法摘錄) triplets in various solutions of (方程式無法摘錄) also agree with the model of the OSC formation.
• 中文關鍵字： NMP relaxation in Cr(acac)3 solutions; outer sphere complex formation
• 英文關鍵字： --