Photoracemization and excited state relaxation through non-adiabatic pathways in chromium (III) oxalate ions.
Photoracemization and excited state relaxation through non-adiabatic pathways in chromium (III) oxalate ions.
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通过草酸铬 (III) 离子的非绝热途径进行光外消旋化和激发态弛豫。
DOI：
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发表时间：
2012
影响因子：
4.4
通讯作者：
M. Paterson
中科院分区：
文献类型：
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作者：
Justyna M. Żurek;M. Paterson
对开壳草酸铬[Cr(C(2)O(4))(3)](3-)离子的光化学及其非绝热弛豫途径进行了计算研究。连接(4)T态和(4)A(2)基态的准Jahn-Teller型尖锥交点的存在解释了观察到的光致外消旋。这涉及其中一个铬-氧键的断裂，络合物形成一个不稳定的三角双金字塔形式，连接两个基态立体异构体和激发的四重态流形。位于(4)T态和下位(2)E态之间的系间交叉缝可以猝灭四重态反应并导致(2)E→(4)A(2)发射。
Computational studies on the photochemistry of the open-shell chromium oxalate [Cr(C(2)O(4))(3)](3-) ion, including its non-adiabatic relaxation pathways, have been performed. The presence of the peaked conical intersection of a quasi-Jahn-Teller type, connecting the (4)T state with (4)A(2) ground state, accounts for the observed photoinduced racemization. This involves the rupture of one of the Cr-O bonds and the complex forms an unstable trigonal bipyramid form that connects both ground state stereoisomers with the excited quartet manifold. Intersystem crossing seams have been located between the (4)T and lower lying (2)E state which can quench the quartet reaction and lead to (2)E → (4)A(2) emission.