Watching Photoinduced Chemistry and Molecular Energy Flow in Solution in Real Time

Aßmann, J.; Kling, Matthias F.; Abel, Bernd

doi:10.1002/anie.200200541

Cited by 54 publications

(70 citation statements)

References 164 publications

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“…As a background of this model, recent experimental studies on IVR in solution indicated the IVR rates are well explained by such a hierarchical or tier model [1,[14][15][16][17][18]. In the tier model, the initial vibrational energy is not distributed over all the vibrational modes simultaneously, but flows through specific low-order couplings step by step.…”

Section: Resultsmentioning

confidence: 99%

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Solvent-assisted intramolecular vibrational energy redistribution of S1 perylene in ketone solvents

Kiba

Sato

Akimoto

et al. 2006

Journal of Photochemistry and Photobiology A: Chemistry

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We investigated vibrational energy relaxations of S 1 perylene at an excess energy of ca. 2800 cm -1 in several ketone solvents by femtosecond time-resolved fluorescence measurements.Temporal evolution of fluorescence emissions occurs on the following distinct timescales: 70 ~ 330 fs, 0.6 ~ 1.1 ps and 1.8 ~ 4.9 ps. The latter two was assigned to the intramolecular vibrational redistribution (IVR), and to the solvent-assisted IVR (SA-IVR), respectively. In SA-IVR, intramolecular vibrational couplings are affected by elastic or quasi-elastic interactions between solute and solvents. Solvent dependence of the SA-IVR rates can be explained qualitatively by the tier V-V coupling mechanism.

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Section: Resultsmentioning

confidence: 99%

“…Flow of excess vibrational energy of molecules and solvation dynamics are closely related to each other, and play important roles in various photochemical reactions in condensed phases [1][2].…”

Section: Introductionmentioning

confidence: 99%

Solvent-assisted intramolecular vibrational energy redistribution of S1 perylene in ketone solvents

Kiba

Sato

Akimoto

et al. 2006

Journal of Photochemistry and Photobiology A: Chemistry

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“…Numerous studies have sought to explore the relative importance of IVR and IET in excited molecules in solution, and both processes are commonly encapsulated in the general term, vibrational energy transfer (VET). 16,17 The timescales for VET are sensitively dependent on the mode of interest (isolated high frequency modes typically relax more slowly than low frequency vibrations) and on the strength of the solute-solvent interaction. 16 In the case of strongly interacting systems (e.g.…”

Section: Introductionmentioning

confidence: 99%

Comparing molecular photofragmentation dynamics in the gas and liquid phases

Harris

Murdock

Zhang

et al. 2013

Phys. Chem. Chem. Phys.

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This article explores the extent to which insights gleaned from detailed studies of molecular photodissociations in the gas phase (i.e. under isolated molecule conditions) can inform our understanding of the corresponding photofragmentation processes in solution. Systems selected for comparison include a thiophenol (p-methylthiophenol), a thioanisole (p-methylthioanisole) and phenol, in vacuum and in cyclohexane solution.UV excitation in the gas phase results in RX-Y (X = O, S; Y = H, CH 3 ) bond fission in all cases, but over timescales that vary by B4 orders of magnitude -all of which behaviours can be rationalised on the basis of the relevant bound and dissociative excited state potential energy surfaces (PESs) accessed by UV photoexcitation, and of the conical intersections that facilitate radiationless transfer between these PESs. Timeresolved UV pump-broadband UV/visible probe and/or UV pump-broadband IR probe studies of the corresponding systems in cyclohexane solution reveal additional processes that are unique to the condensed phase. Thus, for example, the data clearly reveal evidence of (i) vibrational relaxation of the photoexcited molecules prior to their dissociation and of the radical fragments formed upon X-Y bond fission, and (ii) geminate recombination of the RX and Y products (leading to reformation of the ground state parent and/or isomeric adducts). Nonetheless, the data also show that, in each case, the characteristics (and the timescale) of the initial bond fission process that occurs under isolated molecule conditions are barely changed by the presence of a weakly interacting solvent like cyclohexane. These condensed phase studies are then extended to an ether analogue of phenol (allyl phenyl ether), wherein UV photo-induced RO-allyl bond fission constitutes the first step of a photo-Claisen rearrangement.

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“…Since these original studies, the field of femtochemistry has rapidly evolved and it is not the aim of this perspective to review this development. Rather, the reader is referred to a number of excellent articles, reviews and books that have appeared over the years (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15).…”

Section: Introductionmentioning

confidence: 99%

Electronic structure in real time: mapping valence electron rearrangements during chemical reactions

Wernet

2011

Phys. Chem. Chem. Phys.

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The interest in following the evolution of the valence electronic structure of atoms and molecules during chemical reactions on a femtosecond time scale is discussed. By explicitly mapping the occupied part of the electronic structure with femtosecond pump-probe schemes one essentially follows the electrons making the bonds while the bonds change. This holds the key to unprecedented insight into chemical bonding in short-lived intermediates and reveals the coupled motion of electrons and nuclei. Examples from the recent literature on small molecules and anionic clusters in the gas phase and on atoms and molecules on surfaces using lab-based femtosecond laser methods are used to demonstrate the case. They highlight how the evolution of the valence electronic structure can be probed with time-resolved photoelectron spectroscopy with ultraviolet (UV) probe photon energies of up to 6 eV. It is shown how new insight can be gained by extending the probing wavelength into the vacuumultraviolet (VUV) region to photon energies of 20 eV and more by accessing the whole occupied valence electronic structure with time-resolved VUV photoelectron spectroscopy.Finally, the importance of soft x-ray free-electron lasers with probe photon energies of several hundred eV and femtosecond pulses and in particular the key role of femtosecond timeresolved soft x-ray emission spectroscopy or resonant inelastic x-ray scattering for mapping the electronic structure during chemical reactions is discussed.2

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Watching Photoinduced Chemistry and Molecular Energy Flow in Solution in Real Time

Cited by 54 publications

References 164 publications

Solvent-assisted intramolecular vibrational energy redistribution of S1 perylene in ketone solvents

Solvent-assisted intramolecular vibrational energy redistribution of S1 perylene in ketone solvents

Comparing molecular photofragmentation dynamics in the gas and liquid phases

Electronic structure in real time: mapping valence electron rearrangements during chemical reactions

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