On the prospects of optical cycling in diatomic cations: effects of transition metals, spin–orbit couplings, and multiple bonds
On the prospects of optical cycling in diatomic cations: effects of transition metals, spin–orbit couplings, and multiple bonds
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DOI：
10.1080/00268976.2022.2107582
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发表时间：
2022-08
影响因子：
1.7
通讯作者：
P. Wójcik;E. Hudson;A. Krylov
中科院分区：
文献类型：
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作者：
P. Wójcik;E. Hudson;A. Krylov
具有光学循环中心（OCCs）的分子在基础研究和应用（例如量子计算）的背景下是非常可取的，因为它们可以通过重复吸收和发射（因此，循环）有效地冷却到非常低的温度。带电物种为实验控制和操作提供了额外的优势。我们提出了一系列双原子自由基阳离子的系统计算研究，这些双原子自由基阳离子由一个d嵌段金属和一个p嵌段配体组成，它们与成功的激光冷却的中性分子是等电子的（在它们的价壳中）。利用高阶电子结构方法，我们表征了低洼电子态的状态和跃迁性质，并计算了frank - condon因子。计算的分支比和辐射寿命表明，在阳离子中，类似于在中性分子的激光冷却中成功使用的电子跃迁不是最佳的。我们提出了适合于光循环的替代跃迁，并强调了有助于未来在带电或中性分子中设计OCCs的趋势。图形抽象
Molecules with optical cycling centres (OCCs) are highly desirable in the context of fundamental studies as well as applications (e.g. quantum computing) because they can be effectively cooled to very low temperatures by repeated absorption and emission (hence, cycling). Charged species offer additional advantages for experimental control and manipulation. We present a systematic computational study of a series of diatomic radical-cations made of a d-block metal and a p-block ligand, that are isoelectronic (in their valence shell) to the successfully laser-cooled neutral molecules. Using high-level electronic structure methods, we characterise state and transition properties of low-lying electronic states and compute Franck–Condon factors. The computed branching ratios and radiative lifetimes reveal that the electronic transitions analogous to those successfully used in the laser cooling of neutral molecules are less than optimal in the cations. We propose alternative transitions suitable for optical cycling and highlight trends that could assist future designs of OCCs in charged or neutral molecules. GRAPHICAL ABSTRACT