Acioli Paulo H, Zhang Xinxing, Bowen Kit H, Jellinek Julius
Department of Physics, Northeastern Illinois University, Chicago, Illinois 60625, United States.
Collaborative Innovation Center of Chemical Sciences and Engineering, College of Chemistry, Nankai University, Tianjin 300071, China.
J Phys Chem A. 2022 Jul 7;126(26):4241-4247. doi: 10.1021/acs.jpca.2c03116. Epub 2022 Jun 24.
Results of size-selected electron photo-detachment experiments and density functional theory calculations on anionic AlPt, = 1-7, clusters are presented and analyzed. The measured and calculated spectra of electron binding energies are, overall, in excellent accord with each other. The analysis reveals the general importance of accounting for the multiplicity of structural forms of a given-size cluster that can contribute to its measured spectrum, especially when the clusters are fluxional and/or the conditions of the experiment allow for structural transitions. We show that for the systems studied here, the size-specific peculiarities of the measured spectra can be understood in terms of the combined contributions of corresponding different accessible stable equilibrium conformations, transition-state configurations, and electronic-crossing structures that may play the role of effective barriers in electronically nonadiabatic dynamics.
本文给出并分析了对阴离子AlPt（n = 1 - 7）团簇进行的尺寸选择电子光解离实验结果和密度泛函理论计算结果。电子结合能的测量光谱和计算光谱总体上吻合得非常好。分析表明，考虑给定尺寸团簇可能对其测量光谱有贡献的多种结构形式具有普遍重要性，特别是当团簇具有流动性和/或实验条件允许结构转变时。我们表明，对于此处研究的体系，测量光谱的尺寸特异性特征可以通过相应不同可及稳定平衡构象、过渡态构型以及可能在电子非绝热动力学中起有效势垒作用的电子交叉结构的综合贡献来理解。
