Response theory calculations of the singlet–triplet transition probabilities in the HOCl molecule
Response theory calculations of the singlet–triplet transition probabilities in the HOCl molecule
复制标题
HOCl分子中单重态-三重态跃迁概率的响应理论计算
DOI：
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
H. Ågren
中科院分区：
文献类型：
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作者：
B. Minaev;H. Ågren
高氯酸盐分子在平流层光化学中的作用很大程度上依赖于它在长波区(λ300 nm)的光解作用。为了预测单-三重态吸收在该分子中可能的重要性，我们对基单重态X1a‘和激发三重态3A“和3A’进行了几何优化，并用二次响应理论计算了不同弯曲角和O-Cl距离下的单重态-三重态跃迁几率，说明了自旋-轨道耦合算符的完整形式。在这些计算结果的基础上，讨论了3A“←X1a‘和3A’←X1a‘吸收在高氯酸光解中的重要性。
The role of the HOCl molecule in stratospheric photochemistry is highly dependent on its photolysis in the long wavelengthregion (λ 300 nm). In order to predict the possible importance of the singlet–triplet absorption in this molecule we haveperformed geometry optimizations of the ground singlet X1A′ and the excited triplet 3A″ and 3A′ states, and performed quadraticresponse theory calculations of the singlet–triplet transition probabilities at different bending angles and O–Cl distances, accounting for the complete form of the spin–orbit coupling operator. Based on the results of these calculations the importance of the 3A″ ← X1A′ and 3A′ ← X1A′ absorption in HOCl photolysis is discussed.