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| In addition to the trans isomer, photoexcitation of cis-stilbene generates the cyclic product 4a,4b-dihydrophenanthrene in 10% yield. The yields of the three processes add up to ~1, suggesting that only one pathway may be available for the deactivation excited stilbene. Trans-stilbene is thermodynamically more stable; however, the barrier to thermal isomerization is significantly larger than that of AB, and the rate of thermal isomerization at room temperature is very slow.Dynamic simulations and ab initio lculations predict isomerization of stilbene to be dominated by rotation, with some contribution from skeletal deformations. A crossover point between S1 and S0 states has been located near a torsional angle of 90. Both trans and cis-stilbene must acquire the same conformation prior to S0 ←S1 intersystem crossing; however a small barrier exists on the side of the trans isomer. As a result, the S1 state of trans-stilbene has a considerably longer lifetime than that of the cis isomer. Ultrafast timeresolved spectroscopy has revealed S0←S1 relaxation of stilbene to be unimodal. |
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wskk: 金幣+10, 翻譯EPI+1, ★★★★★最佳答案, 謝謝你了 2015-04-21 11:16:28
wskk: 金幣+10, 翻譯EPI+1, ★★★★★最佳答案, 謝謝你了 2015-04-21 11:16:28
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In addition to the trans isomer, photoexcitation of cis-stilbene generates the cyclic product 4a,4b-ihydrophenanthrene in 10% yield. 除了反式異構體，順勢光激勵也能生成環(huán)狀產物4a,4b-二氫菲（產率為10%）。 The yields of the three processes add up to ~1, suggesting that only one pathway may be available for the deactivation excited stilbene. 三個步驟的產率增加到了 ~1，這就標明，其中只有一個方法能夠鈍化刺激的對稱二苯代乙烯。 Trans-stilbene is thermodynamically more stable; however, the barrier to thermal isomerization is significantly larger than that of AB, and the rate of thermal isomerization at room temperature is very slow. 雖然二苯乙烯的熱力學穩(wěn)定性更高，然而，其熱異構化的困難比實現(xiàn)AB異構化的困難要大得多，而且在室溫環(huán)境中，熱異構化速率非常慢。 Dynamic simulations and ab initio calculations predict isomerization of stilbene to be dominated by rotation, with some contribution from skeletal deformations. 受骨骼形變的啟發(fā)，動態(tài)仿真和從頭計算法預測，對稱二苯代乙烯異構將由分子旋轉完成。 A crossover point between S1 and S0 states has been located near a torsional angle of 90. Both trans and cis-stilbene must acquire the same conformation prior to S0 ←S1 intersystem crossing; however a small barrier exists on the side of the trans isomer. 經過定位，S1和S0質檢的交叉點接近于90度的扭轉角。在系統(tǒng)由S1穿越到S0之前，無論順式和反式異構都必須有同樣的構象；其中對于反式異構體，這存在一點小小的困難。 As a result, the S1 state of trans-stilbene has a considerably longer lifetime than that of the cis isomer. Ultrafast timeresolved spectroscopy has revealed S0←S1 relaxation of stilbene to be unimodal. 因此，比起順式異構體，反式-二苯乙烯的S1狀態(tài)相當?shù)拈L。 極速時間分辨光譜法標明，對稱二苯代乙烯又S1狀態(tài)緩沖到S0狀態(tài)是單向的。 |
4樓2015-04-21 10:33:08
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