Our previous studies (Shields et al 2020 J. Phys. B: At. Mol. Opt. Phys. 53 125101; Shields et al 2020 Euro. Phys. J. D 74 191) have predicted that the atom-fullerene hybrid photoionization properties for X = Cl, Br and I endohedrally confined in C₆₀ are different before and after an electron transfers from C₆₀ to the halogen. It was further found as a rule that the ionization dynamics is insensitive to the C₆₀ level the electron originates from to produce X ⁻@ C60+ . In the current study, we report an exception to this rule in F@C₆₀. It is found that when the electron vacancy is situated in the C₆₀ level that participates in the hybridization in F⁻@ C60+ , the mixing becomes dramatically large leading to strong modifications in the photoionization of the hybrid levels. This novel effect is fundamentally based on a level-crossing phenomenon driven by the electron transfer in F@C₆₀. But when the vacancy is at any other pure level of C₆₀, the level-invariance is retained showing weak hybridization. Even though this case of F@C₆₀ is an exception in the halogen@C₆₀ series, the phenomenon can be more general and can occur with compounds of other atoms caged in a variety of fullerenes. Possible experimental studies are suggested to benchmark the present results.

中文翻译：

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F−@ C60+ 分子的电子空位依赖性杂化光电离：一种新效应

我们之前的研究（Shields等人2020J.物理学。乙：在。摩尔。选择。物理。53125101；盾牌等人2020欧元。物理。J.D 74191) 预测原子-富勒烯杂化光电离特性X_{= C 60}内嵌限制的Cl、Br和I在电子从C ₆₀转移到卤素之前和之后是不同的。进一步发现，电离动力学通常对产生电子的C _{60能级不敏感}X ^- @ C60+ . 在当前的研究中，我们在 F@C ₆₀中报告了此规则的例外情况。发现当电子空位位于C ₆₀能级时参与F ⁻ @中的杂化 C60+ ，混合变得非常大，导致混合能级的光电离发生强烈变化。这种新颖的效果基本上是基于由 F@C ₆₀中的电子转移驱动的水平交叉现象。但当空位处于C ₆₀的任何其他纯能级时，能级不变性得以保留，表明弱杂交。尽管 F@C ₆₀的这种情况是 halogen@C ₆₀系列中的一个例外，但这种现象可能更为普遍，并且可能发生在其他原子被笼罩在各种富勒烯中的化合物中。建议进行可能的实验研究以对目前的结果进行基准测试。