Generic Mechanism of Optimal Energy Transfer Efficiency: A Scaling Theory of the Mean First-Passage Time in Exciton Systems
An asymptotic scaling theory is presented using the conceptual basis of trapping-free subspace (i.e., orthogonal subspace) to establish the generic mechanism of optimal efficiency of excitation energy transfer in light-harvesting systems. A quantum state orthogonal to the trap will exhibit noise-ass...
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| Format: | Article |
| Language: | en_US |
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American Physical Society
2013
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| Online Access: | http://hdl.handle.net/1721.1/79649 https://orcid.org/0000-0001-7616-7809 |
| _version_ | 1811080631602380800 |
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| author | Wu, Jianlan Silbey, Robert J. Cao, Jianshu |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Wu, Jianlan Silbey, Robert J. Cao, Jianshu |
| author_sort | Wu, Jianlan |
| collection | MIT |
| description | An asymptotic scaling theory is presented using the conceptual basis of trapping-free subspace (i.e., orthogonal subspace) to establish the generic mechanism of optimal efficiency of excitation energy transfer in light-harvesting systems. A quantum state orthogonal to the trap will exhibit noise-assisted transfer, clarifying the significance of initial preparation. For such an initial state, the efficiency is enhanced in the weak damping limit (⟨t⟩∼1/Γ), and suppressed in the strong damping limit (⟨t⟩∼Γ), analogous to Kramers turnover in classical rate theory. An interpolating expression ⟨t⟩=A/Γ+B+CΓ quantitatively describes the trapping time over the entire range of the dissipation strength, and predicts the optimal efficiency at Γ[subscript opt]∼J for homogenous systems. In the presence of static disorder, the scaling law of transfer time with respect to dephasing rate changes from linear to square root, suggesting a weaker dependence on the environment. The prediction of the scaling theory is verified in a symmetric dendrimer system by numerically exact quantum calculations. Though formulated in the context of excitation energy transfer, the analysis and conclusions apply in general to open quantum processes, including electron transfer, fluorescence emission, and heat conduction. |
| first_indexed | 2024-09-23T11:34:21Z |
| format | Article |
| id | mit-1721.1/79649 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T11:34:21Z |
| publishDate | 2013 |
| publisher | American Physical Society |
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| spelling | mit-1721.1/796492022-09-27T20:23:36Z Generic Mechanism of Optimal Energy Transfer Efficiency: A Scaling Theory of the Mean First-Passage Time in Exciton Systems Wu, Jianlan Silbey, Robert J. Cao, Jianshu Massachusetts Institute of Technology. Department of Chemistry Wu, Jianlan Silbey, Robert J. Cao, Jianshu An asymptotic scaling theory is presented using the conceptual basis of trapping-free subspace (i.e., orthogonal subspace) to establish the generic mechanism of optimal efficiency of excitation energy transfer in light-harvesting systems. A quantum state orthogonal to the trap will exhibit noise-assisted transfer, clarifying the significance of initial preparation. For such an initial state, the efficiency is enhanced in the weak damping limit (⟨t⟩∼1/Γ), and suppressed in the strong damping limit (⟨t⟩∼Γ), analogous to Kramers turnover in classical rate theory. An interpolating expression ⟨t⟩=A/Γ+B+CΓ quantitatively describes the trapping time over the entire range of the dissipation strength, and predicts the optimal efficiency at Γ[subscript opt]∼J for homogenous systems. In the presence of static disorder, the scaling law of transfer time with respect to dephasing rate changes from linear to square root, suggesting a weaker dependence on the environment. The prediction of the scaling theory is verified in a symmetric dendrimer system by numerically exact quantum calculations. Though formulated in the context of excitation energy transfer, the analysis and conclusions apply in general to open quantum processes, including electron transfer, fluorescence emission, and heat conduction. National Science Foundation (U.S.) (Grant CHE-1112825) United States. Defense Advanced Research Projects Agency (Grant N66001-10-1-4063) United States. Dept. of Energy (Center for Excitonics Grant DE-SC0001088) 2013-07-22T16:43:11Z 2013-07-22T16:43:11Z 2013-05 2012-07 Article http://purl.org/eprint/type/JournalArticle 0031-9007 1079-7114 http://hdl.handle.net/1721.1/79649 Wu, Jianlan, Robert J. Silbey, and Jianshu Cao. Generic Mechanism of Optimal Energy Transfer Efficiency: A Scaling Theory of the Mean First-Passage Time in Exciton Systems. Physical Review Letters 110, no. 20 (May 2013). © 2013 American Physical Society https://orcid.org/0000-0001-7616-7809 en_US http://dx.doi.org/10.1103/PhysRevLett.110.200402 Physical Review Letters Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Physical Society APS |
| spellingShingle | Wu, Jianlan Silbey, Robert J. Cao, Jianshu Generic Mechanism of Optimal Energy Transfer Efficiency: A Scaling Theory of the Mean First-Passage Time in Exciton Systems |
| title | Generic Mechanism of Optimal Energy Transfer Efficiency: A Scaling Theory of the Mean First-Passage Time in Exciton Systems |
| title_full | Generic Mechanism of Optimal Energy Transfer Efficiency: A Scaling Theory of the Mean First-Passage Time in Exciton Systems |
| title_fullStr | Generic Mechanism of Optimal Energy Transfer Efficiency: A Scaling Theory of the Mean First-Passage Time in Exciton Systems |
| title_full_unstemmed | Generic Mechanism of Optimal Energy Transfer Efficiency: A Scaling Theory of the Mean First-Passage Time in Exciton Systems |
| title_short | Generic Mechanism of Optimal Energy Transfer Efficiency: A Scaling Theory of the Mean First-Passage Time in Exciton Systems |
| title_sort | generic mechanism of optimal energy transfer efficiency a scaling theory of the mean first passage time in exciton systems |
| url | http://hdl.handle.net/1721.1/79649 https://orcid.org/0000-0001-7616-7809 |
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