Experimental probing of conical intersection dynamics in the photodissociation of thioanisole

Lim, Jae S.; Kim, Sang Kyu

doi:10.1038/nchem.702

Cited by 124 publications

(127 citation statements)

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“…Most reported experiments have indirect circumstantial evidence of their presence, by probing the fast dynamics of a vibrational wave packet passing through a conical intersection 8,42 or via the product branching ratio 43 . Ultrafast femtosecond techniques can locate the CoIn with resolution of a few tens of femtoseconds 44 .…”

Section: Discussionmentioning

confidence: 99%

Monitoring conical intersections in the ring opening of furan by attosecond stimulated X-ray Raman spectroscopy

Hua

Oesterling

Biggs

et al. 2015

Structural Dynamics

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Attosecond X-ray pulses are short enough to capture snapshots of molecules undergoing nonadiabatic electron and nuclear dynamics at conical intersections (CoIns). We show that a stimulated Raman probe induced by a combination of an attosecond and a femtosecond pulse has a unique temporal and spectral resolution for probing the nonadiabatic dynamics and detecting the ultrafast (∼4.5 fs) passage through a CoIn. This is demonstrated by a multiconfigurational self-consistent-field study of the dynamics and spectroscopy of the furan ring-opening reaction. Trajectories generated by surface hopping simulations were used to predict Attosecond Stimulated X-ray Raman Spectroscopy signals at reactant and product structures as well as representative snapshots along the conical intersection seam. The signals are highly sensitive to the changes in nonadiabatically coupled electronic structure and geometry.

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Section: Discussionmentioning

confidence: 99%

Monitoring conical intersections in the ring opening of furan by attosecond stimulated X-ray Raman spectroscopy

Hua

Oesterling

Biggs

et al. 2015

Structural Dynamics

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“…26 Detailed setup for the velocity map ion imaging had been described earlier. 11,12 Images were averaged for 100 000-720 000 laser shots. For the mass analyzed threshold ionization (MATI) spectroscopy, the excitation laser pulse in the range of 280-290 nm and the ionization laser pulse in the 327-355 nm range were generated by frequency doubling of two independently tunable dye laser outputs pumped by the second harmonic output of a Nd:YAG laser (Continuum, Precision 2).…”

Section: Methodsmentioning

confidence: 99%

“…This determination, however, can allow for a powerful shortcut in understanding nonadiabatic chemical reactions wherein the full knowledge and elucidation of the whole complex multi-dimensional potential energy surfaces are not required. The structure and dynamic role of the conical intersection have been subjected to intensive theoretical [2][3][4][5][6][7][8][9] and experimental studies [10][11][12][13][14][15][16][17][18][19][20][21][22][23] for decades. Despite numerous successful theoretical and experimental studies, however, chemists still keenly undertake probing of the conical intersection region more directly.…”

Section: Introductionmentioning

confidence: 99%

Conical intersection seam and bound resonances embedded in continuum observed in the photodissociation of thioanisole-d3

Han

Lim

Yoon

et al. 2014

The Journal of Chemical Physics

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Herein, the multi-dimensional nature of the conical intersection seam has been experimentally revealed in the photodissociation reaction of thioanisole-d3 (C6H5SCD3) excited on S1, giving C6H5S·(Ã or X̃]) +·CD3 products. The translational energy distribution of the nascent·CD3 fragment, reflecting the relative yields of the C6H5S·(Ã) and C6H5S·(X̃) products, was measured at each S1 vibronic band using the velocity map ion imaging technique. Direct access of the reactant flux to the conical intersection seam leads to the increase of the nonadiabatic transition probability resulting in sharp resonances in the X̃/ÃC6H5S·product branching ratio at several distinct S1 vibronic bands. The nature of the S1 vibronic bands associated with such dynamic resonances was clarified by the mass-analyzed threshold ionization spectroscopy. The bound state embedded in continuum generated by the conical intersection is observed as a distinct dynamic resonance, revealing the nature of the nuclear motion responsible for the nonadiabatic coupling of two potential energy surfaces at the conical intersection. The multi-dimensional facets of the conical intersection seam in terms of its detailed structure and dynamic role are discussed with the aid of theoretical calculations.

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“…87 Exciting thioanisole on a few select parent absorption resonances in a narrow energy range above the S 1 -S 0 origin results in very different Ã / X state product ratios. 88,91 These 'dynamic resonances' are pictured as transitions to bound states embedded in the continuum generated by the conical intersection; their identification may provide insights into the nuclear motions that facilitate non-adiabatic coupling at CI-1 and/or CI-2. 92 Not surprisingly, phenol, thiophenol and thioanisole are attracting much interest as test-systems for honing the treatment of non-adiabatic effects in molecular photodissociations.…”

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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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Experimental probing of conical intersection dynamics in the photodissociation of thioanisole

Cited by 124 publications

References 31 publications

Monitoring conical intersections in the ring opening of furan by attosecond stimulated X-ray Raman spectroscopy

Monitoring conical intersections in the ring opening of furan by attosecond stimulated X-ray Raman spectroscopy

Conical intersection seam and bound resonances embedded in continuum observed in the photodissociation of thioanisole-d3

Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

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