Five-Membered Rings Create Off-Zero Modes in Nanographene
The low-energy electronic structure of nanographenes can be tuned through zero-energy pi-electron states, typically referred to as zero-modes. Customizable electronic and magnetic structures have been engineered by coupling zero-modes through exchange and hybridization interactions. Manipulation of the energy of such states, however, has not yet received significant attention. We find that attaching a five-membered ring to a zigzag edge hosting a zero-mode perturbs the energy of that mode and turns it into an off-zero mode: a localized state with a distinctive electron-accepting character. Whereas the end states of typical 7-atom-wide armchair graphene nanoribbons (7-AGNRs) lose their electrons when physisorbed on Au(111) (due to its high work function), converting them into off-zero modes by introducing cyclopentadienyl five-membered rings allows them to retain their single-electron occupation. This approach enables the magnetic properties of 7-AGNR end states to be explored using scanning tunneling microscopy (STM) on a gold substrate. We find a gradual decrease of the magnetic coupling between off-zero mode end states as a function of GNR length, and evolution from a more closed-shell to a more open-shell ground state.
WOS:001136361000001
2023-12-05
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Funder | Grant Number |
Nederlandse Organisatie voor Wetenschappelijk Onderzoek | DE-AC02-05-CH11231 |
US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division | N00014-19-1-2503 |
Office of Naval Research | CHE-2204252 |
National Science Foundation | 019.182EN.18 |
Dutch Research Council through the Rubicon Award | |
National Defense Science and Engineering Graduate Fellowship | 172543 |
Swiss National Science Foundation | s1146 |
Swiss National Supercomputing Centre (CSCS) | |
Center of EPFL | S10OD024998 |
NIH | |