Periodic trends in electron transport through extended metal atom chains: comparison of Ru-3(dpa)(4)(NCS)(2) with its first-row analogues
Density functional theory is used to reconcile the structural, magnetic and electron transport properties of a triruthenium extended metal atom chain, Ru 3(dpa) 4(NCS) 2. The distinct bending of the Ru-Ru-Ru core in this species is traced to strong second-order mixing between levels of σ and π symme...
| Main Authors: | , , |
|---|---|
| Format: | Journal article |
| Language: | English |
| Published: |
2012
|
| _version_ | 1826294613490532352 |
|---|---|
| author | Mohan, P Georgiev, V McGrady, J |
| author_facet | Mohan, P Georgiev, V McGrady, J |
| author_sort | Mohan, P |
| collection | OXFORD |
| description | Density functional theory is used to reconcile the structural, magnetic and electron transport properties of a triruthenium extended metal atom chain, Ru 3(dpa) 4(NCS) 2. The distinct bending of the Ru-Ru-Ru core in this species is traced to strong second-order mixing between levels of σ and π symmetry that are near degenerate in the linear geometry. The dominant electron transport channel is formed by the LUMO, an orbital of π* symmetry that lies just above the Fermi level of the gold electrode. The bending has a substantial impact on electron transport in that it induces a spin crossover from a quintet to a singlet which in turn brings the LUMO much closer to the Fermi level. The presence of significant net π bonding in the metal chains also broadens the π/π nb/π* manifold, such that the channel is not strongly perturbed by the electric field, even at a bias of 1.0 V. The presence of a robust π symmetry conduction channel marks the triruthenium systems out as quite distinct from its first-row counterparts, Cr 3(dpa) 4(NCS) 2 and Co 3(dpa) 4(NCS) 2, where current flows primarily through the σ framework. This journal is © 2012 The Royal Society of Chemistry. |
| first_indexed | 2024-03-07T03:48:22Z |
| format | Journal article |
| id | oxford-uuid:c0526684-aeba-45ab-9a45-1a43445d0737 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T03:48:22Z |
| publishDate | 2012 |
| record_format | dspace |
| spelling | oxford-uuid:c0526684-aeba-45ab-9a45-1a43445d07372022-03-27T05:53:39ZPeriodic trends in electron transport through extended metal atom chains: comparison of Ru-3(dpa)(4)(NCS)(2) with its first-row analoguesJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:c0526684-aeba-45ab-9a45-1a43445d0737EnglishSymplectic Elements at Oxford2012Mohan, PGeorgiev, VMcGrady, JDensity functional theory is used to reconcile the structural, magnetic and electron transport properties of a triruthenium extended metal atom chain, Ru 3(dpa) 4(NCS) 2. The distinct bending of the Ru-Ru-Ru core in this species is traced to strong second-order mixing between levels of σ and π symmetry that are near degenerate in the linear geometry. The dominant electron transport channel is formed by the LUMO, an orbital of π* symmetry that lies just above the Fermi level of the gold electrode. The bending has a substantial impact on electron transport in that it induces a spin crossover from a quintet to a singlet which in turn brings the LUMO much closer to the Fermi level. The presence of significant net π bonding in the metal chains also broadens the π/π nb/π* manifold, such that the channel is not strongly perturbed by the electric field, even at a bias of 1.0 V. The presence of a robust π symmetry conduction channel marks the triruthenium systems out as quite distinct from its first-row counterparts, Cr 3(dpa) 4(NCS) 2 and Co 3(dpa) 4(NCS) 2, where current flows primarily through the σ framework. This journal is © 2012 The Royal Society of Chemistry. |
| spellingShingle | Mohan, P Georgiev, V McGrady, J Periodic trends in electron transport through extended metal atom chains: comparison of Ru-3(dpa)(4)(NCS)(2) with its first-row analogues |
| title | Periodic trends in electron transport through extended metal atom chains: comparison of Ru-3(dpa)(4)(NCS)(2) with its first-row analogues |
| title_full | Periodic trends in electron transport through extended metal atom chains: comparison of Ru-3(dpa)(4)(NCS)(2) with its first-row analogues |
| title_fullStr | Periodic trends in electron transport through extended metal atom chains: comparison of Ru-3(dpa)(4)(NCS)(2) with its first-row analogues |
| title_full_unstemmed | Periodic trends in electron transport through extended metal atom chains: comparison of Ru-3(dpa)(4)(NCS)(2) with its first-row analogues |
| title_short | Periodic trends in electron transport through extended metal atom chains: comparison of Ru-3(dpa)(4)(NCS)(2) with its first-row analogues |
| title_sort | periodic trends in electron transport through extended metal atom chains comparison of ru 3 dpa 4 ncs 2 with its first row analogues |
| work_keys_str_mv | AT mohanp periodictrendsinelectrontransportthroughextendedmetalatomchainscomparisonofru3dpa4ncs2withitsfirstrowanalogues AT georgievv periodictrendsinelectrontransportthroughextendedmetalatomchainscomparisonofru3dpa4ncs2withitsfirstrowanalogues AT mcgradyj periodictrendsinelectrontransportthroughextendedmetalatomchainscomparisonofru3dpa4ncs2withitsfirstrowanalogues |