Translational, rotational and vibrational relaxation dynamics of a solute molecule in a non-interacting solvent

Grubb, Michael P.; Coulter, Philip; Marroux, Hugo J. B.; Hornung, B.; McMullen, Ryan S.; Orr-Ewing, Andrew J.; Ashfold, Michael N. R.

doi:10.1038/nchem.2570

Cited by 17 publications

(15 citation statements)

References 29 publications

(29 reference statements)

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“…We recently established that (small molecule) solute rotation is relatively unhindered in PFC solutions, leading to the observation of significant rotational band structure in the absorption spectrum. 16 The degree to which the solute rotation is hindered in each solvent provides further insights about the local solute environment. Further discussion of this effect is provided in the ESI ‡…”

Section: Resultsmentioning

confidence: 99%

Unravelling the mechanisms of vibrational relaxation in solution

et al. 2017

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Section: Resultsmentioning

confidence: 99%

Unravelling the mechanisms of vibrational relaxation in solution

et al. 2017

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“…Recent studies of BrCN photolysis in perfluorohexane -an essentially non-interacting solvent -represent an extreme exemplar of this statement. 108 But the foregoing examples also highlight the need for care when making such extrapolations. The dissociation of an isolated gas-phase molecule constitutes a closed problem; energy, linear and angular momentum are conserved.…”

Section: 100mentioning

confidence: 99%

Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

Ashfold

Murdock

Oliver

2017

Annu. Rev. Phys. Chem.

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This is the submitted manuscript. The final published version (version of record) is available online via Annual Review of Physical Chemistry at http://www.annualreviews.org/doi/10.1146/annurev-physchem-052516-050756 . Please refer to any applicable terms of use of the publisher University of Bristol -Explore Bristol Research General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/pure/about/ebr-terms 1 Molecular Photofragmentation Dynamics in the Gas and Condensed PhasesMichael N.R. Ashfold, Daniel Murdock and Thomas A.A. Oliver School of Chemistry, University of Bristol, Bristol, U.K., BS8 1TS AbstractExciting a molecule with a UV photon often leads to bond fission, but the final outcome of the bond cleavage is typically both molecule and phase dependent. The photodissociation of an isolated gasphase molecule can be viewed as closed system: energy and momentum are conserved, and the fragmentation is irreversible. The same is not true in a solution-phase photodissociation process.Solvent interactions may dissipate some of the photoexcitation energy prior to bond fission, and will dissipate any excess energy partitioned into the dissociation products. Products that have no analogue in the corresponding gas-phase study may arise by, for example, geminate recombination. Here we illustrate the extents to which dynamical insights from gas-phase studies can inform our understanding of the corresponding solution-phase photochemistry and how, in the specific case of photoinduced ring-opening reactions, solution-phase studies can in some cases reveal dynamical insights more clearly than the corresponding gas-phase study.Keywords photochemistry, photodissociation, photoinduced ring opening, non-adiabatic dynamics, conical intersections. 2 HISTORICAL CONTEXTCiamician is recognised as a pioneer of (organic) photochemistry and an early advocate for fuel production by means of artificial photo'synthesis'. 1 His studies were performed in solution and usually driven by sunlight, at a time when the concept of the photon was yet to be fully accepted.Identifying the ultimate reaction products was in itself a major achievement, and any ideas regarding reaction mechanism were rudimentary. Even the concatenation of ideas like ground and excited electronic states, radiative and non-radiative transitions, spin multiplicity, etc, into what would later be termed a Jablonski diagram 2 still lay far in the future.A potentially more fruitful path at that time for those curious about the mechanisms of photochemical reactions was to focus on very simple molecular systems -diatomic and 'diatomic-like' molecules. generally polychromatic) light sources were now available, and the development of grating spectrometers enabled the recording of electronic absorption spectra for many small gas-phase molecules. Vibrational and even rotational fine structure was resolved and interpreted in many such ...

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“…This invariance suggests minimal interaction with the solvent. The observation of only one component of the band suggests a hindered rotation of the molecule in the solvent cage 28 . A kinetic trace of the integrated absorbance of the peak, fitted to an exponential rise function, indicates a sub-microsecond rise of the reaction byproduct.…”

Section: Resultsmentioning

confidence: 94%

Picosecond to millisecond tracking of a photocatalytic decarboxylation reaction provides direct mechanistic insights

et al. 2019

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The photochemical decarboxylation of carboxylic acids is a versatile route to free radical intermediates for chemical synthesis. However, the sequential nature of this multi-step reaction renders the mechanism challenging to probe. Here, we employ a 100 kHz mid-infrared probe in a transient absorption spectroscopy experiment to track the decarboxylation of cyclohexanecarboxylic acid in acetonitrile-d3 over picosecond to millisecond timescales using a photooxidant pair (phenanthrene and 1,4-dicyanobenzene). Selective excitation of phenanthrene at 256 nm enables a diffusion-limited photoinduced electron transfer to 1,4-dicyanobenzene. A measured time offset in the rise of the CO2 byproduct reports on the lifetime (520 ± 120 ns) of a reactive carboxyl radical in solution, and spectroscopic observation of the carboxyl radical confirm its formation as a reaction intermediate. Precise clocking of the lifetimes of radicals generated in situ by an activated C-C bond fission will pave the way for improving the photocatalytic selectivity and turnover.

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Translational, rotational and vibrational relaxation dynamics of a solute molecule in a non-interacting solvent

Cited by 17 publications

References 29 publications

Unravelling the mechanisms of vibrational relaxation in solution

Unravelling the mechanisms of vibrational relaxation in solution

Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

Picosecond to millisecond tracking of a photocatalytic decarboxylation reaction provides direct mechanistic insights

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