Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion
We develop a hybrid cumulant expansion method to account for the system-bath entanglement in the emission spectrum in the multi-chromophoric Förster transfer rate. In traditional perturbative treatments, the emission spectrum is usually expanded with respect to the system-bath coupling term in both...
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| Format: | Article |
| Language: | en_US |
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American Institute of Physics (AIP)
2017
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| Online Access: | http://hdl.handle.net/1721.1/110442 https://orcid.org/0000-0001-7616-7809 |
| _version_ | 1826207153078140928 |
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| author | Ma, Jian Moix, Jeremy Cao, Jianshu |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Ma, Jian Moix, Jeremy Cao, Jianshu |
| author_sort | Ma, Jian |
| collection | MIT |
| description | We develop a hybrid cumulant expansion method to account for the system-bath entanglement in the emission spectrum in the multi-chromophoric Förster transfer rate. In traditional perturbative treatments, the emission spectrum is usually expanded with respect to the system-bath coupling term in both real and imaginary time. This perturbative treatment gives a reliable absorption spectrum, where the bath is Gaussian and only the real-time expansion is involved. For the emission spectrum, the initial state is an entangled state of the system plus bath. Traditional perturbative methods are problematic when the excitations are delocalized and the energy gap is larger than the thermal energy, since the second-order expansion cannot predict the displacement of the bath. In the present method, the real-time dynamics is carried out by using the 2nd-order cumulant expansion method, while the displacement of the bath is treated more accurately by utilizing the exact reduced density matrix of the system. In a sense, the hybrid cumulant expansion is based on a generalized version of linear response theory with entangled initial states. |
| first_indexed | 2024-09-23T13:44:52Z |
| format | Article |
| id | mit-1721.1/110442 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:44:52Z |
| publishDate | 2017 |
| publisher | American Institute of Physics (AIP) |
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| spelling | mit-1721.1/1104422022-09-28T15:54:21Z Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion Ma, Jian Moix, Jeremy Cao, Jianshu Massachusetts Institute of Technology. Department of Chemistry Ma, Jian Moix, Jeremy Cao, Jianshu We develop a hybrid cumulant expansion method to account for the system-bath entanglement in the emission spectrum in the multi-chromophoric Förster transfer rate. In traditional perturbative treatments, the emission spectrum is usually expanded with respect to the system-bath coupling term in both real and imaginary time. This perturbative treatment gives a reliable absorption spectrum, where the bath is Gaussian and only the real-time expansion is involved. For the emission spectrum, the initial state is an entangled state of the system plus bath. Traditional perturbative methods are problematic when the excitations are delocalized and the energy gap is larger than the thermal energy, since the second-order expansion cannot predict the displacement of the bath. In the present method, the real-time dynamics is carried out by using the 2nd-order cumulant expansion method, while the displacement of the bath is treated more accurately by utilizing the exact reduced density matrix of the system. In a sense, the hybrid cumulant expansion is based on a generalized version of linear response theory with entangled initial states. 2017-07-05T13:55:22Z 2017-07-05T13:55:22Z 2015-03 2014-08 Article http://purl.org/eprint/type/JournalArticle 0021-9606 1089-7690 http://hdl.handle.net/1721.1/110442 Ma, Jian; Moix, Jeremy and Cao, Jianshu. “Förster Resonance Energy Transfer, Absorption and Emission Spectra in Multichromophoric Systems. II. Hybrid Cumulant Expansion.” Journal of Chemical Physics 142, 9 (March 2015): 094107 © 2015 AIP Publishing LLC https://orcid.org/0000-0001-7616-7809 en_US http://dx.doi.org/10.1063/1.4908600 Journal of Chemical Physics 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 Institute of Physics (AIP) MIT web domain |
| spellingShingle | Ma, Jian Moix, Jeremy Cao, Jianshu Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion |
| title | Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion |
| title_full | Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion |
| title_fullStr | Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion |
| title_full_unstemmed | Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion |
| title_short | Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion |
| title_sort | forster resonance energy transfer absorption and emission spectra in multichromophoric systems ii hybrid cumulant expansion |
| url | http://hdl.handle.net/1721.1/110442 https://orcid.org/0000-0001-7616-7809 |
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