Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States
The ultrafast dynamics of 1,3-cyclohexadiene has been investigated via structurally sensitive Rydberg electron binding energies and shown to differ upon excitation to the 1B state and the 3p Rydberg state. Excitation of the molecule with 4.63 eV photons into the ultrashort-lived 1B state yields the...
| Main Authors: | , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
Hindawi Publishing Corporation
2015
|
| Online Access: | http://hdl.handle.net/1721.1/96245 |
| _version_ | 1811081789815390208 |
|---|---|
| author | Buhler, Christine C. Minitti, Michael P. Deb, Sanghamitra Bao, Jie Weber, Peter M. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Buhler, Christine C. Minitti, Michael P. Deb, Sanghamitra Bao, Jie Weber, Peter M. |
| author_sort | Buhler, Christine C. |
| collection | MIT |
| description | The ultrafast dynamics of 1,3-cyclohexadiene has been investigated via structurally sensitive Rydberg electron binding energies and shown to differ upon excitation to the 1B state and the 3p Rydberg state. Excitation of the molecule with 4.63 eV photons into the ultrashort-lived 1B state yields the well-known ring opening to 1,3,5-hexatriene, while a 5.99 eV photon lifts the molecule directly into the 3p-Rydberg state. Excitation to 3p does not induce ring opening. In both experiments, time-dependent shifts of the Rydberg electron binding energy reflect the structural dynamics of the molecular core. Structural distortions associated with 3p-excitation cause a dynamical shift in the p[subscript 𝑥]- and p[subscript 𝑦]-binding energies by 10 and 26 meV/ps, respectively, whereas after excitation into 1B, more severe structural transformations along the ring-opening coordinate produce shifts at a rate of 40 to 60 meV/ps. The experiment validates photoionization-photoelectron spectroscopy via Rydberg states as a powerful technique to observe structural dynamics of polyatomic molecules. |
| first_indexed | 2024-09-23T11:52:30Z |
| format | Article |
| id | mit-1721.1/96245 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T11:52:30Z |
| publishDate | 2015 |
| publisher | Hindawi Publishing Corporation |
| record_format | dspace |
| spelling | mit-1721.1/962452022-09-27T22:30:31Z Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States Buhler, Christine C. Minitti, Michael P. Deb, Sanghamitra Bao, Jie Weber, Peter M. Massachusetts Institute of Technology. Department of Chemistry Bao, Jie The ultrafast dynamics of 1,3-cyclohexadiene has been investigated via structurally sensitive Rydberg electron binding energies and shown to differ upon excitation to the 1B state and the 3p Rydberg state. Excitation of the molecule with 4.63 eV photons into the ultrashort-lived 1B state yields the well-known ring opening to 1,3,5-hexatriene, while a 5.99 eV photon lifts the molecule directly into the 3p-Rydberg state. Excitation to 3p does not induce ring opening. In both experiments, time-dependent shifts of the Rydberg electron binding energy reflect the structural dynamics of the molecular core. Structural distortions associated with 3p-excitation cause a dynamical shift in the p[subscript 𝑥]- and p[subscript 𝑦]-binding energies by 10 and 26 meV/ps, respectively, whereas after excitation into 1B, more severe structural transformations along the ring-opening coordinate produce shifts at a rate of 40 to 60 meV/ps. The experiment validates photoionization-photoelectron spectroscopy via Rydberg states as a powerful technique to observe structural dynamics of polyatomic molecules. United States. Dept. of Energy. Office of Basic Energy Sciences (Division of Chemical Sciences, Geosciences, and Biosciences Grant DE-FG02-03ER15452) 2015-03-30T15:41:03Z 2015-03-30T15:41:03Z 2011 2011-05 2015-03-26T09:32:58Z Article http://purl.org/eprint/type/JournalArticle 1687-9228 1687-9236 http://hdl.handle.net/1721.1/96245 Buhler, Christine C., Michael P. Minitti, Sanghamitra Deb, Jie Bao, and Peter M. Weber. “Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States.” Journal of Atomic, Molecular, and Optical Physics 2011 (2011): 1–6. en http://dx.doi.org/10.1155/2011/637593 Journal of Atomic, Molecular, and Optical Physics Creative Commons Attribution http://creativecommons.org/licenses/by/2.0 Copyright © 2011 Christine C. Bühler et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. application/pdf Hindawi Publishing Corporation Hindawi Publishing Corporation |
| spellingShingle | Buhler, Christine C. Minitti, Michael P. Deb, Sanghamitra Bao, Jie Weber, Peter M. Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States |
| title | Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States |
| title_full | Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States |
| title_fullStr | Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States |
| title_full_unstemmed | Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States |
| title_short | Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States |
| title_sort | ultrafast dynamics of 1 3 cyclohexadiene in highly excited states |
| url | http://hdl.handle.net/1721.1/96245 |
| work_keys_str_mv | AT buhlerchristinec ultrafastdynamicsof13cyclohexadieneinhighlyexcitedstates AT minittimichaelp ultrafastdynamicsof13cyclohexadieneinhighlyexcitedstates AT debsanghamitra ultrafastdynamicsof13cyclohexadieneinhighlyexcitedstates AT baojie ultrafastdynamicsof13cyclohexadieneinhighlyexcitedstates AT weberpeterm ultrafastdynamicsof13cyclohexadieneinhighlyexcitedstates |