{"title":"苯的光电子角分布:不对称参数是否可以作为基准?","authors":"M.H. Ribas , J.M.H. Fófano , M.G.P. Homem , M.M. Fujimoto","doi":"10.1016/j.elspec.2024.147441","DOIUrl":null,"url":null,"abstract":"<div><p>The calculated asymmetry parameter (<span><math><mi>β</mi></math></span>) and photoionisation cross sections for eight outermost orbitals (<span><math><mrow><mn>1</mn><msub><mrow><mi>e</mi></mrow><mrow><mn>1</mn><mi>g</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>3</mn><msub><mrow><mi>e</mi></mrow><mrow><mn>2</mn><mi>g</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>1</mn><msub><mrow><mi>a</mi></mrow><mrow><mn>2</mn><mi>u</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>3</mn><msub><mrow><mi>e</mi></mrow><mrow><mn>1</mn><mi>u</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>1</mn><msub><mrow><mi>b</mi></mrow><mrow><mn>2</mn><mi>u</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>2</mn><msub><mrow><mi>b</mi></mrow><mrow><mn>1</mn><mi>u</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>3</mn><msub><mrow><mi>a</mi></mrow><mrow><mn>1</mn><mi>g</mi></mrow></msub></mrow></math></span>, and <span><math><mrow><mn>2</mn><msub><mrow><mi>e</mi></mrow><mrow><mn>2</mn><mi>g</mi></mrow></msub></mrow></math></span>) of benzene, in the gas phase, are presented in the range from threshold to 35 eV. The Schwinger Variational Method with Padé approximants was employed to generate the continuum wavefunction of photoelectrons and the dipole matrix transition was computed in the velocity (<span><math><mi>V</mi></math></span>) and length (<span><math><mi>L</mi></math></span>) approach of the dipole operator. This operator in <span><math><mi>V</mi></math></span> or <span><math><mi>L</mi></math></span> form does not affect significantly <span><math><mi>β</mi></math></span> values in the energy range studied. The cross sections in <span><math><mi>V</mi></math></span> form produce lower magnitudes than <span><math><mi>L</mi></math></span> and are closer to the measurements. The resonance peaks were observed in the cross sections for some orbitals and their positions were not affected by the dipole approach. Finally, symmetry analysis is done on the partial cross sections to assign the main contributing final state to the resonance feature and also link this to the minimum in the asymmetry parameter. The comparison of our results with other theories has, in general, good qualitative and some quantitative agreement. For some orbitals (<span><math><mrow><mn>1</mn><msub><mrow><mi>a</mi></mrow><mrow><mn>2</mn><mi>u</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>2</mn><msub><mrow><mi>b</mi></mrow><mrow><mn>1</mn><mi>u</mi></mrow></msub></mrow></math></span>), severe disagreements between theory and experiment are highlighted. Some possible causes for these differences are pointed out. Because of this, we conclude that some asymmetry parameters and PICS for benzene, in ionisation studies, cannot yet be considered as a benchmark and will be necessary further investigation to clarify such discrepancies.</p></div>","PeriodicalId":15726,"journal":{"name":"Journal of Electron Spectroscopy and Related Phenomena","volume":"273 ","pages":"Article 147441"},"PeriodicalIF":1.8000,"publicationDate":"2024-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Photoelectron angular distribution of benzene: Can the asymmetry parameter be considered a benchmark?\",\"authors\":\"M.H. Ribas , J.M.H. Fófano , M.G.P. Homem , M.M. Fujimoto\",\"doi\":\"10.1016/j.elspec.2024.147441\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The calculated asymmetry parameter (<span><math><mi>β</mi></math></span>) and photoionisation cross sections for eight outermost orbitals (<span><math><mrow><mn>1</mn><msub><mrow><mi>e</mi></mrow><mrow><mn>1</mn><mi>g</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>3</mn><msub><mrow><mi>e</mi></mrow><mrow><mn>2</mn><mi>g</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>1</mn><msub><mrow><mi>a</mi></mrow><mrow><mn>2</mn><mi>u</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>3</mn><msub><mrow><mi>e</mi></mrow><mrow><mn>1</mn><mi>u</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>1</mn><msub><mrow><mi>b</mi></mrow><mrow><mn>2</mn><mi>u</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>2</mn><msub><mrow><mi>b</mi></mrow><mrow><mn>1</mn><mi>u</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>3</mn><msub><mrow><mi>a</mi></mrow><mrow><mn>1</mn><mi>g</mi></mrow></msub></mrow></math></span>, and <span><math><mrow><mn>2</mn><msub><mrow><mi>e</mi></mrow><mrow><mn>2</mn><mi>g</mi></mrow></msub></mrow></math></span>) of benzene, in the gas phase, are presented in the range from threshold to 35 eV. The Schwinger Variational Method with Padé approximants was employed to generate the continuum wavefunction of photoelectrons and the dipole matrix transition was computed in the velocity (<span><math><mi>V</mi></math></span>) and length (<span><math><mi>L</mi></math></span>) approach of the dipole operator. This operator in <span><math><mi>V</mi></math></span> or <span><math><mi>L</mi></math></span> form does not affect significantly <span><math><mi>β</mi></math></span> values in the energy range studied. The cross sections in <span><math><mi>V</mi></math></span> form produce lower magnitudes than <span><math><mi>L</mi></math></span> and are closer to the measurements. The resonance peaks were observed in the cross sections for some orbitals and their positions were not affected by the dipole approach. Finally, symmetry analysis is done on the partial cross sections to assign the main contributing final state to the resonance feature and also link this to the minimum in the asymmetry parameter. The comparison of our results with other theories has, in general, good qualitative and some quantitative agreement. For some orbitals (<span><math><mrow><mn>1</mn><msub><mrow><mi>a</mi></mrow><mrow><mn>2</mn><mi>u</mi></mrow></msub></mrow></math></span>, <span><math><mrow><mn>2</mn><msub><mrow><mi>b</mi></mrow><mrow><mn>1</mn><mi>u</mi></mrow></msub></mrow></math></span>), severe disagreements between theory and experiment are highlighted. Some possible causes for these differences are pointed out. Because of this, we conclude that some asymmetry parameters and PICS for benzene, in ionisation studies, cannot yet be considered as a benchmark and will be necessary further investigation to clarify such discrepancies.</p></div>\",\"PeriodicalId\":15726,\"journal\":{\"name\":\"Journal of Electron Spectroscopy and Related Phenomena\",\"volume\":\"273 \",\"pages\":\"Article 147441\"},\"PeriodicalIF\":1.8000,\"publicationDate\":\"2024-04-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Electron Spectroscopy and Related Phenomena\",\"FirstCategoryId\":\"101\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0368204824000240\",\"RegionNum\":4,\"RegionCategory\":\"物理与天体物理\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"SPECTROSCOPY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Electron Spectroscopy and Related Phenomena","FirstCategoryId":"101","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0368204824000240","RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"SPECTROSCOPY","Score":null,"Total":0}
引用次数: 0
摘要
文中给出了气相中苯的八个最外层轨道(1e1g、3e2g、1a2u、3e1u、1b2u、2b1u、3a1g 和 2e2g)在阈值至 35 eV 范围内的不对称参数 (β)和光电离截面的计算结果。采用帕代近似的施温格变分法生成光电子的连续波函数,并以偶极子算子的速度(V)和长度(L)方法计算偶极子矩阵转换。在所研究的能量范围内,V 或 L 形式的算子不会对 β 值产生显著影响。V 形式的横截面比 L 形式的横截面产生的数值更低,也更接近测量结果。在某些轨道的横截面上可以观察到共振峰,它们的位置不受偶极子方法的影响。最后,我们对部分截面进行了对称分析,以确定共振特征的主要最终状态,并将其与不对称参数的最小值联系起来。总的来说,我们的结果与其他理论的比较具有良好的定性和定量一致性。对于某些轨道(1a2u、2b1u),理论与实验之间存在严重分歧。我们指出了造成这些差异的一些可能原因。因此,我们得出结论,在电离研究中,苯的某些不对称参数和 PICS 尚不能被视为基准,有必要进一步研究以澄清这些差异。
Photoelectron angular distribution of benzene: Can the asymmetry parameter be considered a benchmark?
The calculated asymmetry parameter () and photoionisation cross sections for eight outermost orbitals (, , , , , , , and ) of benzene, in the gas phase, are presented in the range from threshold to 35 eV. The Schwinger Variational Method with Padé approximants was employed to generate the continuum wavefunction of photoelectrons and the dipole matrix transition was computed in the velocity () and length () approach of the dipole operator. This operator in or form does not affect significantly values in the energy range studied. The cross sections in form produce lower magnitudes than and are closer to the measurements. The resonance peaks were observed in the cross sections for some orbitals and their positions were not affected by the dipole approach. Finally, symmetry analysis is done on the partial cross sections to assign the main contributing final state to the resonance feature and also link this to the minimum in the asymmetry parameter. The comparison of our results with other theories has, in general, good qualitative and some quantitative agreement. For some orbitals (, ), severe disagreements between theory and experiment are highlighted. Some possible causes for these differences are pointed out. Because of this, we conclude that some asymmetry parameters and PICS for benzene, in ionisation studies, cannot yet be considered as a benchmark and will be necessary further investigation to clarify such discrepancies.
期刊介绍:
The Journal of Electron Spectroscopy and Related Phenomena publishes experimental, theoretical and applied work in the field of electron spectroscopy and electronic structure, involving techniques which use high energy photons (>10 eV) or electrons as probes or detected particles in the investigation.