The ultrafast photoinduced ring-opening of 1,3-cyclohexadiene constitutes a textbook example of electrocyclic reactions in organic chemistry and a model for photobiological reactions in vitamin D ...synthesis. Although the relaxation from the photoexcited electronic state during the ring-opening has been investigated in numerous studies, the accompanying changes in atomic distance have not been resolved. Here we present a direct and unambiguous observation of the ring-opening reaction path on the femtosecond timescale and subångström length scale using megaelectronvolt ultrafast electron diffraction. We followed the carbon-carbon bond dissociation and the structural opening of the 1,3-cyclohexadiene ring by the direct measurement of time-dependent changes in the distribution of interatomic distances. We observed a substantial acceleration of the ring-opening motion after internal conversion to the ground state due to a steepening of the electronic potential gradient towards the product minima. The ring-opening motion transforms into rotation of the terminal ethylene groups in the photoproduct 1,3,5-hexatriene on the subpicosecond timescale.
Conformational isomers (conformers) of molecules play a decisive role in biology and organic chemistry. However, experimental methods for investigating chemical reaction dynamics are typically not ...conformer-sensitive. We report on a gas-phase megaelectronvolt ultrafast electron diffraction investigation of α-phellandrene undergoing an electrocyclic ring-opening reaction. We directly imaged the evolution of a specific set of α-phellandrene conformers into the product isomer predicted by the Woodward-Hoffmann rules in real space and time. Our experimental results are in quantitative agreement with nonadiabatic quantum molecular dynamics simulations, which provide considerable detail of how conformation influences the time scale and quantum efficiency of photoinduced ring-opening reactions.
Electrocyclic reactions are characterized by the concerted formation and cleavage of both σ and π bonds through a cyclic structure. This structure is known as a pericyclic transition state for ...thermal reactions and a pericyclic minimum in the excited state for photochemical reactions. However, the structure of the pericyclic geometry has yet to be observed experimentally. We use a combination of ultrafast electron diffraction and excited state wavepacket simulations to image structural dynamics through the pericyclic minimum of a photochemical electrocyclic ring-opening reaction in the molecule α-terpinene. The structural motion into the pericyclic minimum is dominated by rehybridization of two carbon atoms, which is required for the transformation from two to three conjugated π bonds. The σ bond dissociation largely happens after internal conversion from the pericyclic minimum to the electronic ground state. These findings may be transferrable to electrocyclic reactions in general.
Large statistical samples of quasar spectra have previously indicated possible cosmological variations in the fine-structure constant, α. A smaller sample of higher signal-to-noise ratio spectra, ...with dedicated calibration, would allow a detailed test of this evidence. Towards that end, we observed equatorial quasar HS 1549+1919 with three telescopes: the Very Large Telescope, Keck and, for the first time in such analyses, Subaru. By directly comparing these spectra to each other, and by ‘supercalibrating’ them using asteroid and iodine-cell tests, we detected and removed long-range distortions of the quasar spectra's wavelength scales which would have caused significant systematic errors in our α measurements. For each telescope we measure the relative deviation in α from the current laboratory value, Δα/α, in three absorption systems at redshifts z
abs = 1.143, 1.342 and 1.802. The nine measurements of Δα/α are all consistent with zero at the 2σ level, with 1σ statistical (systematic) uncertainties 5.6–24 (1.8–7.0) parts per million (ppm). They are also consistent with each other at the 1σ level, allowing us to form a combined value for each telescope and, finally, a single value for this line of sight: Δα/α = −5.4 ± 3.3stat ± 1.5sys ppm, consistent with both zero and previous, large samples. We also average all Large Programme results measuring Δα/α = −0.6 ± 1.9stat ± 0.9sys ppm. Our results demonstrate the robustness and reliability at the 3 ppm level afforded by supercalibration techniques and direct comparison of spectra from different telescopes.
We present an accurate analysis of the H2 absorption lines from the z
abs ∼ 2.4018 damped Lyα system towards HE 0027−1836 observed with the Very Large Telescope Ultraviolet and Visual Echelle ...Spectrograph (VLT/UVES) as a part of the European Southern Observatory Large Programme 'The UVES large programme for testing fundamental physics' to constrain the variation of proton-to-electron mass ratio, μ ≡ m
p
/m
e
. We perform cross-correlation analysis between 19 individual exposures taken over three years and the combined spectrum to check the wavelength calibration stability. We notice the presence of a possible wavelength-dependent velocity drift especially in the data taken in 2012. We use available asteroids spectra taken with UVES close to our observations to confirm and quantify this effect. We consider single- and two-component Voigt profiles to model the observed H2 absorption profiles. We use both linear regression analysis and Voigt profile fitting where Δμ/μ is explicitly considered as an additional fitting parameter. The two-component model is marginally favoured by the statistical indicators and we get Δμ/μ = −2.5 ± 8.1stat ± 6.2sys ppm. When we apply the correction to the wavelength-dependent velocity drift, we find Δμ/μ = −7.6 ± 8.1stat ± 6.3sys ppm. It will be important to check the extent to which the velocity drift we notice in this study is present in UVES data used for previous Δμ/μ measurements.
The conversion of light into usable chemical and mechanical energy is pivotal to several biological and chemical processes, many of which occur in solution. To understand the structure–function ...relationships mediating these processes, a technique with high spatial and temporal resolutions is required. Here, we report on the design and commissioning of a liquid-phase mega-electron-volt (MeV) ultrafast electron diffraction instrument for the study of structural dynamics in solution. Limitations posed by the shallow penetration depth of electrons and the resulting information loss due to multiple scattering and the technical challenge of delivering liquids to vacuum were overcome through the use of MeV electrons and a gas-accelerated thin liquid sheet jet. To demonstrate the capabilities of this instrument, the structure of water and its network were resolved up to the
3
rd hydration shell with a spatial resolution of 0.6 Å; preliminary time-resolved experiments demonstrated a temporal resolution of 200 fs.
The ability to resolve the dynamics of matter on its native temporal and spatial scales constitutes a key challenge and convergent theme across chemistry, biology, and materials science. The last ...couple of decades have witnessed ultrafast electron diffraction (UED) emerge as one of the forefront techniques with the sensitivity to resolve atomic motions. Increasingly sophisticated UED instruments are being developed that are aimed at increasing the beam brightness in order to observe structural signatures, but so far they have been limited to low average current beams. Here, we present the technical design and capabilities of the HiRES (High Repetition-rate Electron Scattering) instrument, which blends relativistic electrons and high repetition rates to achieve orders of magnitude improvement in average beam current compared to the existing state-of-the-art instruments. The setup utilizes a novel electron source to deliver femtosecond duration electron pulses at up to MHz repetition rates for UED experiments. Instrument response function of sub-500 fs is demonstrated with < 100 fs time resolution targeted in future. We provide example cases of diffraction measurements on solid-state and gas-phase samples, including both micro- and nanodiffraction (featuring 100 nm beam size) modes, which showcase the potential of the instrument for novel UED experiments.
Developing femtosecond resolution methods for directly observing structural dynamics is critical to understanding complex photochemical reaction mechanisms in solution. We have used two recent ...developments, ultrafast mega-electron-volt electron sources and vacuum compatible sub-micron thick liquid sheet jets, to enable liquid-phase ultrafast electron diffraction (LUED). We have demonstrated the viability of LUED by investigating the photodissociation of tri-iodide initiated with a 400 nm laser pulse. This has enabled the average speed of the bond expansion to be measured during the first 750 fs of dissociation and the geminate recombination to be directly captured on the picosecond time scale.
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