Spectral phase effects on nonlinear resonant photochemistry of 1,3-cyclohexadiene in solution

Carroll, Elizabeth C.; Pearson, Brett J.; Florean, Andrei; Bucksbaum, P. H.; Sension, Roseanne J.

doi:10.1063/1.2168454

Cited by 33 publications

(70 citation statements)

References 58 publications

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“…Tunable noncollinear optical parametric amplifiers and programmable acousto-optic pulse shapers were used in this work, together with standard white light ultrafast probe techniques (46,47). The details are discussed in SI Text.…”

Section: Methodsmentioning

confidence: 99%

Control of retinal isomerization in bacteriorhodopsin in the high-intensity regime

Florean

Cardoza

White

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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A learning algorithm was used to manipulate optical pulse shapes and optimize retinal isomerization in bacteriorhodopsin, for excitation levels up to 1.8 ؋ 10 16 photons per square centimeter. Below 1/3 the maximum excitation level, the yield was not sensitive to pulse shape. Above this level the learning algorithm found that a Fourier-transform-limited (TL) pulse maximized the 13-cis population. For this optimal pulse the yield increases linearly with intensity well beyond the saturation of the first excited state. To understand these results we performed systematic searches varying the chirp and energy of the pump pulses while monitoring the isomerization yield. The results are interpreted including the influence of 1-photon and multiphoton transitions. The population dynamics in each intermediate conformation and the final branching ratio between the all-trans and 13-cis isomers are modified by changes in the pulse energy and duration.coherent control ͉ photoisomerization ͉ ultrafast science B acteriorhodopsin (bR) is a photosynthetic protein found in the purple membrane of Halobacterium salinarum and capable of conversion of solar energy into chemical energy. This energy conversion is efficient (1-3) and has several possible applications (4-12). A retinal chromophore is responsible for photon absorption. After photoexcitation retinal undergoes ultrafast isomerization from the all-trans to a 13-cis configuration, accompanied by additional changes in the conformation of bR (3,8). The initial steps of the bR photocycle (see Fig. 1) have been studied intensively (11, 13-33), but there are still unanswered questions regarding the electronic potential energy surfaces (PES) of retinal, the interaction with its surroundings in the protein, and related ultrafast vibrational coupling. A number of models have been proposed, each explaining parts of the large number of experiments (4,13,14,16,(34)(35)(36)(37)(38)(39)(40). Attempts have been made to reconcile the differences between these models (4).We aim to understand how the optical pulse shape and intensity affect the all-trans 3 13-cis yield and to explore potential pathways for producing high photoproduct yields on an ultrafast time scale. This is relevant for energy storage using bio-molecular machines (9, 32). Recently, Prokhorenko et al. showed that the isomerization yield of retinal in bR could be manipulated in a low intensity, biologically relevant regime through the use of phase and amplitude shaped optical fields (25). Modifications of as much as Ϯ20% were observed compared with unshaped pulses capable of exciting an equal number of molecules. Yet the ultimate yields remain small as photon flux was restricted to excite Ϸ0.3% of the chromophores in the excitation volume. In a different experiment, Vogt et al. used much higher intensity, shorter wavelength pump pulses to excite bR and a shaped 800-nm dump pulse to study the evolution of the molecule on the excited state PES (30). They found that the excited population is transferred most effectively back to t...

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Section: Methodsmentioning

confidence: 99%

Control of retinal isomerization in bacteriorhodopsin in the high-intensity regime

Florean

Cardoza

White

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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“…46,47 Finally, and perhaps most importantly, CHD has been used extensively to demonstrate new techniques and concepts. This includes coherent control, both experiment 43,48,49 and theory, 7,50,51 and a range of new ultrafast imaging techniques 52 such as electron diffraction, [53][54][55][56] X-ray scattering, 44,45 Coulomb explosion, 57 and near-edge X-ray absorption fine structure (NEXAFS). 58 The variety of complementary observations generated by these techniques holds great promise for tying down a complete understanding of this important and complex reaction, for instance by combining X-ray scattering and photoelectron data such as in ref.…”

Section: Introductionmentioning

confidence: 99%

Effects of probe energy and competing pathways on time-resolved photoelectron spectroscopy: the ring-opening of 1,3-cyclohexadiene

Tudorovskaya

Minns

Kirrander

2018

Phys. Chem. Chem. Phys.

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The ring-opening dynamics of 1,3-cyclohexadiene (CHD) following UV excitation is studied using a model based on quantum molecular dynamics simulations with the ab initio multiconfigurational Ehrenfest (AI-MCE) method coupled to the Dyson orbital approach for photoionisation cross sections.Time-dependent photoelectron spectra are calculated for probe photon energies in the range 2-15 eV. The calculations demonstrate the value of universal high-energy probes, capable of tracking the dynamics in full, but also the utility of more selective lower-energy probes with a more restricted ionisation range. The predicted signal, especially with the universal probes, becomes highly convoluted due to the contributions from multiple reaction paths, rendering interpretation challenging unless complementary measurements and theoretical comparisons are available.

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“…This process has been extensively studied, in part because of its role in vitamin D biosynthesis. Time-resolved pump-probe techniques have been employed to understand this process [20][21][22][23][24][25]. These studies have found that the conical intersection-mediated ring-opening step in isomerization is completed in less than 200 fs [22], after which the molecule undergoes conformational changes on a range of timescales (see inset in Fig.…”

mentioning

confidence: 99%

Transient X-Ray Fragmentation: Probing a Prototypical Photoinduced Ring Opening

Petrović¹,

Siano²,

White³

et al. 2012

Phys. Rev. Lett.

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Spectral phase effects on nonlinear resonant photochemistry of 1,3-cyclohexadiene in solution

Cited by 33 publications

References 58 publications

Control of retinal isomerization in bacteriorhodopsin in the high-intensity regime

Control of retinal isomerization in bacteriorhodopsin in the high-intensity regime

Effects of probe energy and competing pathways on time-resolved photoelectron spectroscopy: the ring-opening of 1,3-cyclohexadiene

Transient X-Ray Fragmentation: Probing a Prototypical Photoinduced Ring Opening

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