Mechanism of charge transport along zinc porphyrin-based molecular wires.
In this study charge transport along zinc porphyrin-based molecular wires is simulated, considering both bandlike and hopping mechanisms. It is shown that bandlike transport simulations yield significantly overestimated hole mobility values. On the basis of kinetic and thermodynamic considerations,...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
2009
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| _version_ | 1797059015918747648 |
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| author | Kocherzhenko, A Patwardhan, S Grozema, F Anderson, H Siebbeles, L |
| author_facet | Kocherzhenko, A Patwardhan, S Grozema, F Anderson, H Siebbeles, L |
| author_sort | Kocherzhenko, A |
| collection | OXFORD |
| description | In this study charge transport along zinc porphyrin-based molecular wires is simulated, considering both bandlike and hopping mechanisms. It is shown that bandlike transport simulations yield significantly overestimated hole mobility values. On the basis of kinetic and thermodynamic considerations, it is inferred that charge transport along zinc porphyrin-based molecular wires occurs by small polaron hopping. Hole mobility values on the order of 0.1 cm(2) V(-1) s(-1) are found from small polaron hopping simulations, which agree well with previously reported experimental results. It is suggested that the experimentally observed increase of the charge carrier mobility on formation of supramolecular ladderlike structures is determined by two factors. One of these is an increase of charge transfer integrals between monomer units due to molecular wire planarization. A more important factor is the reduction of the amount of energetic disorder along the molecular wire and in its environment. General guidelines for determining the mechanism of charge transport along molecular wires are discussed. |
| first_indexed | 2024-03-06T19:58:16Z |
| format | Journal article |
| id | oxford-uuid:266494d7-5fb8-4a1b-8266-0240c166d3ba |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T19:58:16Z |
| publishDate | 2009 |
| record_format | dspace |
| spelling | oxford-uuid:266494d7-5fb8-4a1b-8266-0240c166d3ba2022-03-26T12:00:41ZMechanism of charge transport along zinc porphyrin-based molecular wires.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:266494d7-5fb8-4a1b-8266-0240c166d3baEnglishSymplectic Elements at Oxford2009Kocherzhenko, APatwardhan, SGrozema, FAnderson, HSiebbeles, LIn this study charge transport along zinc porphyrin-based molecular wires is simulated, considering both bandlike and hopping mechanisms. It is shown that bandlike transport simulations yield significantly overestimated hole mobility values. On the basis of kinetic and thermodynamic considerations, it is inferred that charge transport along zinc porphyrin-based molecular wires occurs by small polaron hopping. Hole mobility values on the order of 0.1 cm(2) V(-1) s(-1) are found from small polaron hopping simulations, which agree well with previously reported experimental results. It is suggested that the experimentally observed increase of the charge carrier mobility on formation of supramolecular ladderlike structures is determined by two factors. One of these is an increase of charge transfer integrals between monomer units due to molecular wire planarization. A more important factor is the reduction of the amount of energetic disorder along the molecular wire and in its environment. General guidelines for determining the mechanism of charge transport along molecular wires are discussed. |
| spellingShingle | Kocherzhenko, A Patwardhan, S Grozema, F Anderson, H Siebbeles, L Mechanism of charge transport along zinc porphyrin-based molecular wires. |
| title | Mechanism of charge transport along zinc porphyrin-based molecular wires. |
| title_full | Mechanism of charge transport along zinc porphyrin-based molecular wires. |
| title_fullStr | Mechanism of charge transport along zinc porphyrin-based molecular wires. |
| title_full_unstemmed | Mechanism of charge transport along zinc porphyrin-based molecular wires. |
| title_short | Mechanism of charge transport along zinc porphyrin-based molecular wires. |
| title_sort | mechanism of charge transport along zinc porphyrin based molecular wires |
| work_keys_str_mv | AT kocherzhenkoa mechanismofchargetransportalongzincporphyrinbasedmolecularwires AT patwardhans mechanismofchargetransportalongzincporphyrinbasedmolecularwires AT grozemaf mechanismofchargetransportalongzincporphyrinbasedmolecularwires AT andersonh mechanismofchargetransportalongzincporphyrinbasedmolecularwires AT siebbelesl mechanismofchargetransportalongzincporphyrinbasedmolecularwires |