Saved in:
| Main Authors: | , , , , , , , , , , , , , , , |
|---|---|
| Format: | Preprint |
| Published: |
2024
|
| Subjects: | |
| Online Access: | https://arxiv.org/abs/2407.21756 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1866910550255992832 |
|---|---|
| author | Li, Juan Mirzanejad, Amir Dong, Wen-Han Liu, Kun Richter, Marcus Wang, Xiao-Ye Berger, Reinhard Du, Shixuan Auwärter, Willi Barth, Johannes V. Ma, Ji Müllen, Klaus Feng, Xinliang Sun, Jia-Tao Muechler, Lukas Palma, Carlos-Andres |
| author_facet | Li, Juan Mirzanejad, Amir Dong, Wen-Han Liu, Kun Richter, Marcus Wang, Xiao-Ye Berger, Reinhard Du, Shixuan Auwärter, Willi Barth, Johannes V. Ma, Ji Müllen, Klaus Feng, Xinliang Sun, Jia-Tao Muechler, Lukas Palma, Carlos-Andres |
| contents | The study of cycloaddition mechanisms is central to the fabrication of extended sp2 carbon nanostructures. Reaction modeling in this context has focused mostly on putative, energetically preferred, exothermic products with limited consideration for symmetry allowed or forbidden mechanistic effects. Here, we introduce a scheme for classifying symmetry-forbidden reaction coordinates in Woodward-Hoffmann correlation diagrams. Topological classifiers grant access to the study of reaction pathways and correlation diagrams in the same footing, for the purpose of elucidating mechanisms and products of polycyclic aromatic azomethine ylide (PAMY) cycloadditions with pentacene-yielding polycyclic aromatic hydrocarbons with an isoindole core in the solid-state and on surfaces as characterized by mass spectrometry and scanning tunneling microscopy, respectively. By means of a tight-binding reaction model and density functional theory (DFT) we find topologically-allowed pathways if a product is endothermic, and topologically-forbidden if a product is exothermic. Our work unveils topological classification as a crucial element for reaction modeling for nanographene engineering, and highlights its fundamental role in the design of cycloadditions in on-surface and solid-state chemical reactions, while underscoring that exothermic pathways can be topologically-forbidden. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2407_21756 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Topological Woodward-Hoffmann classification for cycloadditions in polycyclic aromatic azomethine ylides Li, Juan Mirzanejad, Amir Dong, Wen-Han Liu, Kun Richter, Marcus Wang, Xiao-Ye Berger, Reinhard Du, Shixuan Auwärter, Willi Barth, Johannes V. Ma, Ji Müllen, Klaus Feng, Xinliang Sun, Jia-Tao Muechler, Lukas Palma, Carlos-Andres Chemical Physics The study of cycloaddition mechanisms is central to the fabrication of extended sp2 carbon nanostructures. Reaction modeling in this context has focused mostly on putative, energetically preferred, exothermic products with limited consideration for symmetry allowed or forbidden mechanistic effects. Here, we introduce a scheme for classifying symmetry-forbidden reaction coordinates in Woodward-Hoffmann correlation diagrams. Topological classifiers grant access to the study of reaction pathways and correlation diagrams in the same footing, for the purpose of elucidating mechanisms and products of polycyclic aromatic azomethine ylide (PAMY) cycloadditions with pentacene-yielding polycyclic aromatic hydrocarbons with an isoindole core in the solid-state and on surfaces as characterized by mass spectrometry and scanning tunneling microscopy, respectively. By means of a tight-binding reaction model and density functional theory (DFT) we find topologically-allowed pathways if a product is endothermic, and topologically-forbidden if a product is exothermic. Our work unveils topological classification as a crucial element for reaction modeling for nanographene engineering, and highlights its fundamental role in the design of cycloadditions in on-surface and solid-state chemical reactions, while underscoring that exothermic pathways can be topologically-forbidden. |
| title | Topological Woodward-Hoffmann classification for cycloadditions in polycyclic aromatic azomethine ylides |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2407.21756 |