Lietard Aude, Verlet Jan R R
Department of Chemistry, Durham University, Durham DH1 3LE, United Kingdom.
J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Dolejškova 3, 18223 Prague 8, Czech Republic.
J Phys Chem Lett. 2025 Jul 24;16(29):7307-7312. doi: 10.1021/acs.jpclett.5c01750. Epub 2025 Jul 11.
Electron impact resonances of neutral molecules can be probed using 2D photoelectron spectroscopy of their radical anions, with a core advantage of being able to introduce solvent molecules in a systematic manner through clustering. This approach has been employed previously to probe the effect of water molecules on the resonances of anthracene. Here, we extend this study to probe the resonances of anthracene in the presence of methanol. We find that the nature of the solvent has little impact on the resonances from the perspective of the anion. Only the electron affinity is observed to increase, which corresponds to a concomitant decrease in resonance energy as viewed from a free electron impacting the anthracene-methanol cluster. For a critical cluster size, , the lowest resonance becomes a bound state and the mechanism for electron loss switches from a prompt autodetachment process to a statistical thermionic emission process. We posit that the identity of a general solvent molecule only impacts the stabilization of the resonances of anthracene, which in turn affects the overall decay mechanism and , but the inherent resonance dynamics of anthracene is unaffected by the solvent.
中性分子的电子碰撞共振可以通过其自由基阴离子的二维光电子能谱进行探测，其核心优势在于能够通过聚类系统地引入溶剂分子。此前已采用这种方法来探究水分子对蒽共振的影响。在此，我们将这项研究扩展到探测甲醇存在下蒽的共振。我们发现，从阴离子的角度来看，溶剂的性质对共振影响很小。仅观察到电子亲和能增加，从自由电子撞击蒽 - 甲醇团簇的角度来看，这对应于共振能量的相应降低。对于一个临界团簇尺寸，最低共振变为束缚态，电子损失机制从即时自脱附过程转变为统计热电子发射过程。我们认为，一般溶剂分子的特性仅影响蒽共振的稳定性，进而影响整体衰变机制和，但蒽固有的共振动力学不受溶剂影响。
