Coherent High-Frequency Vibrational Dynamics in the Excited Electronic State of All-Trans Retinal Derivatives
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- 作者：Jan Philip Kraack ; Tiago Buckup ; Marcus Motzkus
- 刊名：The Journal of Physical Chemistry Letters
- 出版年：2013
- 出版时间：February 7, 2013
- 年：2013
- 卷：4
- 期：3
- 页码：383-387
- 全文大小：276K
- 年卷期：v.4,no.3(February 7, 2013)
- ISSN：1948-7185
文摘
Coherent vibrational dynamics of retinal in excited electronic states are of primary importance in the understanding of photobiology. Using pump-DFWM, we demonstrate for the first time the existence of coherent double-bond high-frequency modulations (>1300 cm鈥?) in the excited electronic state of different retinal derivatives. All-trans retinal as well as retinal Schiff bases exhibit a partial frequency downshift of the C鈺怌 double-bond mode from 1580 cm鈥? in the ground state to 1510 cm鈥? in the excited state. In addition, a new vibrational band at 1700 cm鈥? assigned to the C鈺怤 stretching mode in retinal Schiff bases in the excited state is detected. The newly reported bands are observed only in specific spectral regions of excited-state absorption. Implications regarding the observation of vibrational coherences in naturally occurring retinal protonated Schiff bases in rhodopsins are discussed.