{"title":"Breakdown of the molecular orbital picture for X-ray emission of water","authors":"","doi":"10.1016/j.cplett.2024.141583","DOIUrl":null,"url":null,"abstract":"<div><p>By measuring X-ray emission of the water molecule in liquid phase we establish a first example of K-shell X-ray emission spectra with strong breakdown of the molecular orbital picture. A complete splitting of the 2a<span><math><msub><mrow></mrow><mrow><mn>1</mn></mrow></msub></math></span> peak into satellites is observed. A theoretical model with electronic configurations generated by coupled excitations/de-excitations, so-called semi-internal configuration interaction, captures the experimentally recorded features well. Differences with respect to the corresponding breakdown effect in ultraviolet photoelectron spectrum are highlighted. Molecular dynamics calculations indicate that solvent broadening can only make up for a small fraction of the width of the recorded 2a<span><math><msub><mrow></mrow><mrow><mn>1</mn></mrow></msub></math></span> derived band.</p></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":null,"pages":null},"PeriodicalIF":2.8000,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Physics Letters","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0009261424005256","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
By measuring X-ray emission of the water molecule in liquid phase we establish a first example of K-shell X-ray emission spectra with strong breakdown of the molecular orbital picture. A complete splitting of the 2a peak into satellites is observed. A theoretical model with electronic configurations generated by coupled excitations/de-excitations, so-called semi-internal configuration interaction, captures the experimentally recorded features well. Differences with respect to the corresponding breakdown effect in ultraviolet photoelectron spectrum are highlighted. Molecular dynamics calculations indicate that solvent broadening can only make up for a small fraction of the width of the recorded 2a derived band.
通过测量液相中水分子的 X 射线发射，我们首次建立了一个 K 壳 X 射线发射光谱的实例，其分子轨道图被严重破坏。我们观察到 2a1 峰完全分裂成卫星峰。由耦合激发/去激发产生的电子构型（即所谓的半内部构型相互作用）的理论模型很好地捕捉到了实验记录的特征。与紫外光电子能谱中相应的击穿效应的差异得到了强调。分子动力学计算表明，溶剂展宽只能弥补记录的 2a1 导出带宽度的一小部分。
期刊介绍：
Chemical Physics Letters has an open access mirror journal, Chemical Physics Letters: X, sharing the same aims and scope, editorial team, submission system and rigorous peer review.
Chemical Physics Letters publishes brief reports on molecules, interfaces, condensed phases, nanomaterials and nanostructures, polymers, biomolecular systems, and energy conversion and storage.
Criteria for publication are quality, urgency and impact. Further, experimental results reported in the journal have direct relevance for theory, and theoretical developments or non-routine computations relate directly to experiment. Manuscripts must satisfy these criteria and should not be minor extensions of previous work.
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