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Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps towards understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species amongst the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5H)-thiophenone. This strategy provides experimental validation of the predicted high (~50%) yield of an episulfide isomer containing a strained 3-membered ring within ~1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.

Directly imaging structural dynamics involving hydrogen atoms by ultrafast diffraction methods is complicated by their low scattering cross-sections. Here we demonstrate that megaelectronvolt ultrafast electron diffraction is sufficiently sensitive to follow hydrogen dynamics in isolated molecules. In a study of the photodissociation of gas phase ammonia, we simultaneously observe signatures of the nuclear and corresponding electronic structure changes resulting from the dissociation dynamics in the time-dependent diffraction. Both assignments are confirmed by ab initio simulations of the photochemical dynamics and the resulting diffraction observable. While the temporal resolution of the experiment is insufficient to resolve the dissociation in time, our results represent an important step towards the observation of proton dynamics in real space and time.

Electrocyclic reactions are characterized by the concerted formation and cleavage of both {\sigma} and {\pi} 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 {\alpha}-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 {\pi} bonds. The {\sigma} 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., Comment: Combined manuscript and supplementary information

Ultrafast electron diffraction and time-resolved serial crystallography are the basis of the ongoing revolution in capturing at the atomic level of detail the structural dynamics of molecules. However, most experiments employ the classical "ball-and-stick" depictions, and the information of molecular quantum states, such as the density matrix, is missing. Here, we introduce a framework for the preparation and ultrafast coherent diffraction from rotational wave packets of molecules, and we establish a new variant of quantum state tomography for ultrafast electron diffraction to characterize the molecular quantum states. The ability to reconstruct the density matrix of molecules of arbitrary degrees of freedom will provide us with an unprecedentedly clear view of the quantum states of molecules, and enable the visualization of effects dictated by the quantum dynamics of molecules., Comment: arXiv admin note: substantial text overlap with arXiv:2012.11899

Electron scattering on liquid samples has been enabled recently by the development of ultrathin liquid sheet technologies. The data treatment of liquid-phase electron scattering has been mostly reliant on methodologies developed for gas electron diffraction, in which theoretical inputs and empirical fittings are often needed to account for the atomic form factor and remove the inelastic scattering background. The accuracy and impact of these theoretical and empirical inputs has not been benchmarked for liquid-phase electron scattering data. In this work, we present an alternative data treatment method that requires neither theoretical inputs nor empirical fittings. The merits of this new method are illustrated through the retrieval of real-space molecular structure from experimental electron scattering patterns of liquid water, carbon tetrachloride, chloroform, and dichloromethane.

We have investigated the structural dynamics in photoexcited 1,2-diiodotetrafluoroethane molecules (C2F4I2) in the gas phase experimentally using ultrafast electron diffraction and theoretically using FOMO-CASCI excited state dynamics simulations. The molecules are excited by an ultra-violet femtosecond laser pulse to a state characterized by a transition from the iodine 5p orbital to a mixed 5p|| hole and CF2 antibonding orbital, which results in the cleavage of one of the carbon-iodine bonds. We have observed, with sub-Angstrom resolution, the motion of the nuclear wavepacket of the dissociating iodine atom followed by coherent vibrations in the electronic ground state of the C2F4I radical. The radical reaches a stable classical (non-bridged) structure in less than 200 fs., Comment: 13 pages, 11 figures

Observing the motion of the nuclear wavepackets during a molecular reaction, in both space and time, is crucial for understanding and controlling the outcome of photoinduced chemical reactions. We have imaged the motion of a vibrational wavepacket in isolated iodine molecules using ultrafast electron diffraction with relativistic electrons. The time-varying interatomic distance was measured with a precision 0.07 {\AA} and temporal resolution of 230 fs full-width at half-maximum (FWHM). The method is not only sensitive to the position but also the shape of the nuclear wavepacket.

Imaging changes in molecular geometries on their natural femtosecond timescale with sub-Angstrom spatial precision is one of the critical challenges in the chemical sciences, since the nuclear geometry changes determine the molecular reactivity. For photoexcited molecules, the nuclear dynamics determine the photoenergy conversion path and efficiency. We performed a gas-phase electron diffraction experiment using Megaelectronvolt (MeV) electrons, where we captured the rotational wavepacket dynamics of nonadiabatically laser-aligned nitrogen molecules. We achieved an unprecedented combination of 100 fs root-mean-squared (RMS) temporal resolution and sub-Angstrom (0.76 {\AA}) spatial resolution that makes it possible to resolve the position of the nuclei within the molecule. In addition, the diffraction patterns reveal the angular distribution of the molecules, which changes from prolate (aligned) to oblate (anti-aligned) in 300 fs. Our results demonstrate a significant and promising step towards making atomically resolved movies of molecular reactions.

Imaging the structure of molecules in transient excited states remains a challenge due to the extreme requirements for spatial and temporal resolution. Ultrafast electron diffraction from aligned molecules (UEDAM) provides atomic resolution and allows for the retrieval of structural information without the need to rely on theoretical models. Here we use UEDAM and femtosecond laser mass spectrometry (FLMS) to investigate the dynamics in carbon disulfide (CS2) following the interaction with an intense femtosecond laser pulse. We have retrieved images of ground state and excited molecules with 0.03 {\AA} precision. We have observed that the degree of alignment reaches an upper limit at laser intensities below the ionization threshold, and found evidence of structural deformation, dissociation, and ionization at higher laser intensities.

We investigate analytically, numerically, and experimentally the modulational instability in a layered, cubically-nonlinear (Kerr) optical medium that consists of alternating layers of glass and air. We model this setting using a nonlinear Schr\"odinger (NLS) equation with a piecewise constant nonlinearity coefficient and conduct a theoretical analysis of its linear stability, obtaining a Kronig-Penney equation whose forbidden bands correspond to the modulationally unstable regimes. We find very good {\it quantitative} agreement between the theoretical analysis of the Kronig-Penney equation, numerical simulations of the NLS equation, and the experimental results for the modulational instability. Because of the periodicity in the evolution variable arising from the layered medium, we find multiple instability regions rather than just the one that would occur in uniform media., Comment: 13 pages, 12 figures (several with multiple parts); some important changes from the page proof stage implemented in this preprint version

We present the first experimental investigation of modulational instability in a layered Kerr medium. The particularly interesting and appealing feature of our configuration, consisting of alternating glass-air layers, is the piecewise-constant nature of the material properties, which allows a theoretical linear stability analysis leading to a Kronig-Penney equation whose forbidden bands correspond to the modulationally unstable regimes. We find very good {\it quantitative} agreement between theoretical, numerical, and experimental diagnostics of the modulational instability. Because of the periodicity in the evolution variable arising from the layered medium, there are multiple instability regions rather than just one as in the uniform medium., Comment: 4 pages, 4 figures, contains experimental + computational + theoretical results, to appear in Physical Review Letters

We conduct an experimental investigation of nonlinearity management in optics using femtosecond pulses and layered Kerr media consisting of glass and air. By examining the propagation properties over several diffraction lengths, we show that wave collapse can be prevented. We corroborate these experimental results with numerical simulations of the (2 + 1)-dimensional focusing cubic nonlinear Schr\"odinger equation with piecewise constant coefficients and a theoretical analysis of this setting using a moment method., Comment: 4 pages, 4 figures (some with multiple parts; color online), to appear in Physical Review Letters; changes from previous version: revised figures, discussion of time-dependent simulations, other touch-ups