UV-induced unimolecular photochemistry of 2(5H)-furanone and 2(5H)-thiophenone isolated in low temperature inert matrices

Breda, S.; Reva, Igor; Fausto, Rui

doi:10.1016/j.vibspec.2008.07.015

Cited by 21 publications

(22 citation statements)

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“…Of these possible end products, both the aldehyde and enol products require a [1,2]-hydrogen atom migration during their formation. Only the aldehyde product (and various conformers thereof) was implicated in the matrix isolation study of Breda and coworkers, 27 but our calculations indicate that other ring-opened forms are energetically accessible and should be considered. The transition states between the parent molecule and these ring-opened products have also been calculated at the MP2/6-311+G(d,p) level of theory (with subsequent vibrational calculations revealing a single imaginary frequency, highlighting the transition-state nature of these structures).…”

Section: A Structures and Vertical Excitation Energiesmentioning

confidence: 79%

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Transient UV pump–IR probe investigation of heterocyclic ring-opening dynamics in the solution phase: the role played by nσ* states in the photoinduced reactions of thiophenone and furanone

Murdock

Harris

Luke

et al. 2014

Phys. Chem. Chem. Phys.

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The heterocyclic ring-opening dynamics of thiophenone and furanone dissolved in CH3CN have been probed by ultrafast transient infrared spectroscopy. Following irradiation at 267 nm (thiophenone) or 225 nm (furanone), prompt (τ < 1 ps) ring-opening is confirmed by the appearance of a characteristic antisymmetric ketene stretching feature around 2150 cm(-1). The ring-opened product molecules are formed highly vibrationally excited, and cool subsequently on a ∼6.7 ps timescale. By monitoring the recovery of the parent (S0) bleach, it is found that ∼60% of the initially photoexcited thiophenone molecules reform the parent molecule, in stark contrast with the case in furanone where there is less than 10% parent bleach recovery. Complementary ab initio calculations of potential energy cuts along the S-C([double bond, length as m-dash]O) and O-C([double bond, length as m-dash]O) ring-opening coordinate reveals insights into the reaction mechanism, and the important role played by dissociative (n/π)σ* states in the UV-induced photochemistry of such heterocyclic systems.

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Section: A Structures and Vertical Excitation Energiesmentioning

confidence: 79%

“…This assignment is in agreement with that of Breda et al who observed excellent correspondence between their predicted spectrum for the aldehyde (calculated at the B3LYP/6-311++G(d,p) level) and the measured spectrum of their matrix isolated photoproducts, especially in the 500-1500 cm À1 region. 27…”

Section: B Relaxation Pathwaysmentioning

confidence: 99%

Transient UV pump–IR probe investigation of heterocyclic ring-opening dynamics in the solution phase: the role played by nσ* states in the photoinduced reactions of thiophenone and furanone

Murdock

Harris

Luke

et al. 2014

Phys. Chem. Chem. Phys.

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“…The 0.978 scaling factor (below 2500 cm −1 ) is typical and provides an excellent agreement between the theory and experiment in this region. [42][43][44] The 0.946 scaling factor (above 2500 cm −1 ) is lower than usually employed for this level of theory. [45][46][47] The molecules isolated in cryogenic nitrogen matrices usually exhibit OH and NH stretching vibrations at lower frequencies, as compared to the same molecules isolated in an argon matrix.…”

Section: Theoretical Calculationsmentioning

confidence: 93%

Tetrazole acetic acid: Tautomers, conformers, and isomerization

Araujo-Andrade

Reva

Fausto

2014

The Journal of Chemical Physics

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Monomers of (tetrazol-5-yl)-acetic acid (TAA) were obtained by sublimation of the crystalline compound and the resulting vapors were isolated in cryogenic nitrogen matrices at 13 K. The conformational and tautomeric composition of TAA in the matrix was characterized by infrared spectroscopy and vibrational calculations carried out at the B3LYP/6-311++G(d,p) level. TAA may adopt two tautomeric modifications, 1H- and 2H-, depending on the position of the annular hydrogen atom. Two-dimensional potential energy surfaces (PESs) of TAA were theoretically calculated at the MP2/6-311++G(d,p) level, for each tautomer. Four and six symmetry-unique minima were located on these PESs, for 1H- and 2H-TAA, respectively. The energetics of the detected minima was subsequently refined by calculations at the QCISD level. Two 1H- and three 2H-conformers fall within the 0-8 kJ mol(-1) energy range and should be appreciably populated at the sublimation temperature (∼330 K). Observation of only one conformer for each tautomer (1ccc and 2pcc) is explained in terms of calculated barriers to conformational rearrangements. All conformers with the cis O=COH moiety are separated by low barriers (less than 10 kJ mol(-1)) and collapse to the most stable 1ccc (1H-) and 2pcc (2H-) forms during deposition of the matrix. On the trans O=COH surfaces, the relative energies are very high (between 12 and 27 kJ mol(-1)). The trans forms are not thermally populated at the sublimation conditions and were not detected in matrices. One high-energy form in each tautomer, 1cct (1H-) and 2pct (2H-), was found to differ from the most stable form only by rotation of the OH group and separated from other forms by high barriers. This opened a perspective for their stabilization in a matrix. 1cct and 2pct were generated in the matrices selectively by means of narrow-band near-infrared (NIR) irradiations of the samples at 6920 and 6937 cm(-1), where the first OH stretching overtone vibrations of 1ccc and 2pcc occur. The reverse transformations could be induced by irradiations at 7010 and 7030 cm(-1), transforming 1cct and 2pct back to 1ccc and 2pcc, also selectively. Besides the NIR-induced transformations, the photogenerated 1cct and 2pct forms also decay in N2 matrices back to 1ccc and 2pcc spontaneously, with characteristic decay times of hours (1H) and tens of minutes (2H). The decay mechanism is rationalized in terms of the proton tunneling. In crystals, TAA exists exclusively as 1H-tautomer. By contrast, the tautomeric composition of the matrix-isolated monomers was found to consist of both 1H- and 2H-tautomers, in comparable amounts. A mechanistic discussion of the tautomerization process occurring during sublimation, accounting also for the observed minor decomposition of TAA leading to CO2 and 5-methyl-tetrazole, is proposed.

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“…As Figures 4a and 4b show, 267 nm photoexcitation of thiophenone dissolved in acetonitrile leads to an immediate parent bleach signal at ~1685 cm -1 and a broad transient absorption centred at ~2150 cm -1 ; the 'reporter', the carbonyl vibration in thiophenone evolves into a ketene stretch mode upon ring-opening. 127,128 The breadth of the ketene feature, and its subsequent narrowing and blue shift, show that the ring-opened product is formed highly vibrationally excited and then relaxes (within picoseconds) through coupling with the solvent bath. The amplitude of the parent bleach signal decreases with increasing pump-probe delays.…”

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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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UV-induced unimolecular photochemistry of 2(5H)-furanone and 2(5H)-thiophenone isolated in low temperature inert matrices

Cited by 21 publications

References 39 publications

Transient UV pump–IR probe investigation of heterocyclic ring-opening dynamics in the solution phase: the role played by nσ* states in the photoinduced reactions of thiophenone and furanone

Transient UV pump–IR probe investigation of heterocyclic ring-opening dynamics in the solution phase: the role played by nσ* states in the photoinduced reactions of thiophenone and furanone

Tetrazole acetic acid: Tautomers, conformers, and isomerization

Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

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