A brownian oscillator approach to the Kennard−Stepanov relation
The Kennard−Stepanov (KS) relation, also known as the reciprocity relation, connects the absorption and fluorescence spectra of homogeneous complex systems under the assumption of thermal equilibration of the emitting electronic state. A recent elaboration of the theory by Sawicki and Knox (SK) [Phy...
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
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2011
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| Online Access: | https://hdl.handle.net/10356/93963 http://hdl.handle.net/10220/7395 |
| _version_ | 1811689264983834624 |
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| author | Knox, Robert S. Zhao, Yang |
| author2 | School of Materials Science & Engineering |
| author_facet | School of Materials Science & Engineering Knox, Robert S. Zhao, Yang |
| author_sort | Knox, Robert S. |
| collection | NTU |
| description | The Kennard−Stepanov (KS) relation, also known as the reciprocity relation, connects the absorption and fluorescence spectra of homogeneous complex systems under the assumption of thermal equilibration of the emitting electronic state. A recent elaboration of the theory by Sawicki and Knox (SK) [Phys. Rev. A, 1996 54, 4837] introduces a spectral temperature that is a sensitive indicator of the failure of the relation. Studies using the SK formalism, which have been limited almost exclusively to experimental cases, reveal various failures that may be due to incomplete equilibration, inhomogeneity, or both. Using the Brownian oscillator model for nuclear dynamics, we investigate the KS relation theoretically with the aid of the SK spectral temperature. The spectral temperature is again found to be a sensitive indicator, this time of the accuracy of the numerical methods necessary for the multiple integrations. The original KS relation appears to hold regardless of the memory effects of the bath, a result which is not totally unexpected considering the assumptions of excited-state equilibrium implicit in the theory. We extend the theory to the nonequilibrated case of time-resolved fluorescence, where a time-dependent temperature can be defined. |
| first_indexed | 2024-10-01T05:45:21Z |
| format | Journal Article |
| id | ntu-10356/93963 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T05:45:21Z |
| publishDate | 2011 |
| record_format | dspace |
| spelling | ntu-10356/939632020-06-01T10:01:37Z A brownian oscillator approach to the Kennard−Stepanov relation Knox, Robert S. Zhao, Yang School of Materials Science & Engineering DRNTU::Engineering::Materials::Photonics and optoelectronics materials The Kennard−Stepanov (KS) relation, also known as the reciprocity relation, connects the absorption and fluorescence spectra of homogeneous complex systems under the assumption of thermal equilibration of the emitting electronic state. A recent elaboration of the theory by Sawicki and Knox (SK) [Phys. Rev. A, 1996 54, 4837] introduces a spectral temperature that is a sensitive indicator of the failure of the relation. Studies using the SK formalism, which have been limited almost exclusively to experimental cases, reveal various failures that may be due to incomplete equilibration, inhomogeneity, or both. Using the Brownian oscillator model for nuclear dynamics, we investigate the KS relation theoretically with the aid of the SK spectral temperature. The spectral temperature is again found to be a sensitive indicator, this time of the accuracy of the numerical methods necessary for the multiple integrations. The original KS relation appears to hold regardless of the memory effects of the bath, a result which is not totally unexpected considering the assumptions of excited-state equilibrium implicit in the theory. We extend the theory to the nonequilibrated case of time-resolved fluorescence, where a time-dependent temperature can be defined. 2011-12-13T06:48:58Z 2019-12-06T18:48:32Z 2011-12-13T06:48:58Z 2019-12-06T18:48:32Z 2000 2000 Journal Article Zhao, Y., & Knox, R. S. (2000). A Brownian Oscillator Approach to the Kennard-Stepanov Relation. Journal of Physical Chemistry A, 104 (33), 7751–7761. https://hdl.handle.net/10356/93963 http://hdl.handle.net/10220/7395 10.1021/jp001686k en Journal of physical chemistry A © 2000 American Chemical Society |
| spellingShingle | DRNTU::Engineering::Materials::Photonics and optoelectronics materials Knox, Robert S. Zhao, Yang A brownian oscillator approach to the Kennard−Stepanov relation |
| title | A brownian oscillator approach to the Kennard−Stepanov relation |
| title_full | A brownian oscillator approach to the Kennard−Stepanov relation |
| title_fullStr | A brownian oscillator approach to the Kennard−Stepanov relation |
| title_full_unstemmed | A brownian oscillator approach to the Kennard−Stepanov relation |
| title_short | A brownian oscillator approach to the Kennard−Stepanov relation |
| title_sort | brownian oscillator approach to the kennard stepanov relation |
| topic | DRNTU::Engineering::Materials::Photonics and optoelectronics materials |
| url | https://hdl.handle.net/10356/93963 http://hdl.handle.net/10220/7395 |
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