A computational study of radiationless deactivation mechanisms of furan

Stenrup, Michael; Larson, Åsa

doi:10.1016/j.chemphys.2010.10.002

Cited by 36 publications

(40 citation statements)

References 46 publications

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“…1 In order for this process to be competitive with alternative, potentially harmful, photofragmentation/photoisomerisation pathways there must be one or more low energy conical intersections linking the electronically excited state with the ground electronic manifold. 2 One class of conical intersections likely to be important in heterocyclic systems is those lying along a localised ring-bond extension coordinate, which have been implicated in the relaxation dynamics of a series of molecules including furan, [3][4][5][6] thiophene, [7][8][9] psoralen, 10 b-glucose, 11 various substituted spiropyrans, [12][13][14] and DNA bases. 15 Recent work from the Bristol group used transient vibrational absorption (TVA) spectroscopy to investigate the UV-induced relaxation pathways of the heterocyclic a-carbonyl molecules furanone and thiophenone.…”

Section: Introductionmentioning

confidence: 99%

Contrasting ring-opening propensities in UV-excited α-pyrone and coumarin

Murdock

Ingle

Sazanovich

et al. 2016

Phys. Chem. Chem. Phys.

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The photoisomerisation dynamics following excitation to the S1 electronic state of two structurally related heterocyclic molecules, α-pyrone and coumarin, in acetonitrile solution have been probed by time-resolved vibrational absorption spectroscopy. Following irradiation at 310 nm, α-pyrone relaxes rapidly from its initially excited state, with a quantum yield for parent molecule reformation of 68%. Probing the antisymmetric ketene stretch region between 2100 cm(-1) and 2150 cm(-1) confirms the presence of at least two isomeric ring-opened photoproducts, which are formed highly vibrationally excited and relax on a picosecond timescale. Following vibrational cooling, a secondary, thermally driven, isomerisation is observed with a 1.8(1) ns time constant. In contrast, coumarin reforms the parent molecule with essentially 100% efficiency following excitation at 330 nm. The conical intersections driving the non-radiative relaxation of α-pyrone have been investigated using an automated search algorithm. The two lowest energy conical intersections possess remarkably similar structures to the two energetically accessible conical intersections reported previously for coumarin, suggesting that the differing photochemistry is the result of dynamical effects occurring after passage through these intersections.

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Section: Introductionmentioning

confidence: 99%

Contrasting ring-opening propensities in UV-excited α-pyrone and coumarin

Murdock

Ingle

Sazanovich

et al. 2016

Phys. Chem. Chem. Phys.

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“…Indeed, such photo-induced ring-openings have now been explored theoretically in several heterocyclic systems, including furan, [117][118][119] pyrrole, 120 imidazole, 121 2-aminooxazole, 122 adenine, 123 spiropyran, 124,125 and -glucose.…”

Section: Isolated Molecule Dynamicsmentioning

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 work adds to the growing literature highlighting the importance of (n/π)σ * excited states in facilitating both emergent and complete ring opening in heterocyclic molecules. [20][21][22][23][24] …”

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confidence: 99%

Near ultraviolet photochemistry of 2-bromo- and 2-iodothiophene: Revealing photoinduced ring opening in the gas phase?

Marchetti

Karsili

Kelly

et al. 2015

The Journal of Chemical Physics

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Velocity map imaging methods, with a new and improved ion optics design, have been used to explore the near ultraviolet photodissociation dynamics of gas phase 2-bromo- and 2-iodothiophene molecules. In both cases, the ground (X) and spin-orbit excited (X*) (where X = Br, I) atom products formed at the longest excitation wavelengths are found to recoil with fast, anisotropic velocity distributions, consistent with prompt C–X bond fission following excitation via a transition whose dipole moment is aligned parallel to the breaking bond. Upon tuning to shorter wavelengths, this fast component fades and is progressively replaced by a slower, isotropic recoil distribution. Complementary electronic structure calculations provide a plausible explanation for this switch in fragmentation behaviour—namely, the opening of a rival C–S bond extension pathway to a region of conical intersection with the ground state potential energy surface. The resulting ground state molecules are formed with more than sufficient internal energy to sample the configuration space associated with several parent isomers and to dissociate to yield X atom products in tandem with both cyclic and ring-opened partner fragments.

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A computational study of radiationless deactivation mechanisms of furan

Cited by 36 publications

References 46 publications

Contrasting ring-opening propensities in UV-excited α-pyrone and coumarin

Contrasting ring-opening propensities in UV-excited α-pyrone and coumarin

Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

Near ultraviolet photochemistry of 2-bromo- and 2-iodothiophene: Revealing photoinduced ring opening in the gas phase?

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