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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Heteroaryl oxenium ions have diverse and unusual low-energy electronic states
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Heteroaryl oxenium ions have diverse and unusual low-energy electronic states

机译：杂芳基氧离子具有多种不同寻常的低能电子态

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摘要

The electronic state orderings and energies of heteroaryl oxenium ions were computed using high-level CASPT2//CASSCF computations. We find that these ions have a number of diverse, low-energy configurations. Depending on the nature of the heteroaryl substituent, the lowest-energy configuration may be open-shell singlet, closed-shell singlet, or triplet, with further diversity found among the subtypes of these configurations. The 2- and 3-pyridinyl oxenium ions show small perturbations from the phenyl oxenium ion in electronic state orderings and energies, having closed-shell singlet ground states with significant gaps to an n,π* triplet state. In contrast, the 4-pyridinyl oxenium ion is computed to have a low-energy nitrenium ion-like triplet state. The pyrimidinyl oxenium ion is computed to have a near degeneracy between an open-shell singlet and triplet state, and the pyrizidinyl oxenium ion is computed to have a near-triple degeneracy between a closed-shell singlet state, an open-shell singlet state, and a triplet state. Therefore, the ground state of these latter heteroaryl oxenium ions cannot be predicted with certainty; in principle, reactivity from any of these states may be possible. These systems are of fundamental interest for probing the spin- and configuration-dependent reactivity of unusual electronic states for this important class of reactive intermediate.
机译：使用高级CASPT2 // CASSCF计算来计算杂芳基氧鎓离子的电子态有序性和能量。我们发现这些离子具有多种多样的低能构型。取决于杂芳基取代基的性质，最低能量的构型可以是开壳单重态，闭壳单重态或三重态，并且在这些构型的亚型中发现进一步的多样性。 2-和3-吡啶基氧鎓离子在电子态有序和能量方面显示出对苯氧鎓离子的微小扰动，具有闭壳单线态基态，与n，π*三重态具有明显的间隙。相反，计算4-吡啶基yl离子具有低能量的nitr离子样的三重态。计算嘧啶基氧杂鎓离子在开壳单重态和三重态之间具有近简并性，而嘧啶基氧杂鎓离子经计算具有在闭壳单重态，开壳单重态之间近似三重的简并性，和三重态因此，不能确定地预测这些后面的杂芳基氧鎓离子的基态。原则上，来自任何这些状态的反应都是可能的。这些系统对于探测这一重要类别的反应中间体的异常电子态的自旋和构型依赖性反应性具有根本的意义。

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