Implementation and modeling of a femtosecond laser-activated streak camera

8 June 2017) A laser-activated streak camera was built to measure the duration of femtosecond electron pulses. The streak velocity of the device is 1.89 mrad/ps, which corresponds to a sensitivity of 34.9 fs/pixels. The streak camera also measures changes in the relative time of arrival between the laser and electron pulses with a resolution of 70 fs RMS. A full circuit analysis of the structure is presented to describe the streaking field and the general behavior of the device. We have developed a general mathematical model to analyze the streaked images. The model provides an accurate method to extract the pulse duration based on the changes of the electron beam profile when the streaking field is applied

High-resolution movies of molecular rotational dynamics captured with ultrafast electron diffraction

Imaging the structure of molecules during a photoinduced reaction is essential for elucidating reaction mechanisms. This requires high spatiotemporal resolution to capture nuclear motions on the femtosecond and subangstrom scale, and a sufficiently high signal level to sample their continuous evolution with high fidelity. Here we show that, using high-repetition-rate ultrafast electron diffraction, we can accurately reconstruct a movie of the coherent rotational motion of laser-aligned nitrogen molecules. We have used a tabletop 90-keV photoelectron gun to simultaneously achieve high temporal resolution of 240 fs full width at half maximum and an electron beam current that is more than an order of magnitude above the previous state of the art in gas-phase ultrafast electron diffraction. With this, we have made an essentially continuous real-space experimental movie of the rotational motion of the molecular wave packet as it evolves from initial alignment and past multiple revivals. Supplemental materials and 2 videos attached

Ultrafast electron diffraction from transiently aligned asymmetric top molecules: Rotational dynamics and structure retrieval

Ultrafast electron diffraction (UED) from aligned molecules in the gas phase has successfully retrieved structures of both linear and symmetric top molecules. Alignment of asymmetric tops has been recorded with UED but no structural information was retrieved. We present here the extraction of two-dimensional structural information from simple transformations of experimental diffraction patterns of aligned molecules as a proof-of-principle for the recovery of the full structure. We align 4-fluorobenzotrifluoride with a linearly polarized laser and show that we can distinguish between atomic pairs with equal distances that are parallel and perpendicular to the aligned axis. We additionally show with numerical simulations that by cooling the molecules to a rotational temperature of 1 K, more distances and angles can be resolved through direct transformations

Retrieval of the molecular orientation distribution from atom-pair angular distributions

Imaging laser-induced rotational dynamics is an important and active field due to its applications in capturing reactions in the molecular frame and in molecular imaging. Experimental measurement of the molecular orientation distribution, as a function of the Euler angles, has been demonstrated for special cases when the detectable signal is generated along the molecular symmetry axis. Here we developed the general theory that maps the probability density distribution of the molecular orientation to the atom-pair angular distributions for nonlinear molecules. With the theory, the molecular orientation distribution can be retrieved from the measured atom-pair angular distribution, which we demonstrate experimentally using ultrafast electron diffractive imaging of impulsively aligned trifluoro-iodomethane molecules. The retrieved molecular orientation distribution is in good agreement with direct numerical simulations of the time-dependent Schrödinger equation using the experimental conditions. Unlike the existing retrieval methods, the retrieval method does not require solving the Schrödinger equation, works for any alignment method, and is in principle applicable to asymmetric top molecules

Diffractive imaging of dissociation and ground state dynamics in a complex molecule

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 figure

Ultrafast electron diffraction instrument for gas and condensed matter samples

We report the modification of a gas phase ultrafast electron diffraction (UED) instrument that enables experiments with both gas and condensed matter targets, where a time-resolved experiment with sub-picosecond resolution is demonstrated with solid state samples. The instrument relies on a hybrid DC-RF acceleration structure to deliver femtosecond electron pulses on the target, which is synchronized with femtosecond laser pulses. The laser pulses and electron pulses are used to excite the sample and to probe the structural dynamics, respectively. The new system is added with capabilities to perform transmission UED on thin solid samples. It allows for cooling samples to cryogenic temperatures and to carry out time-resolved measurements. We tested the cooling capability by recording diffraction patterns of temperature dependent charge density waves in 1T-TaS2. The time-resolved capability is experimentally verified by capturing the dynamics in photoexcited single-crystal gold

Diffractive imaging of dissociation and ground-state dynamics in a complex molecule

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 ultraviolet femtosecond laser pulse to a state characterized by a transition from the iodine 5p orbital to a mixed 5p||σ 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 wave packet of the dissociating iodine atom followed by coherent vibrations in the electronic ground state of the C2F4I radical. The radical reaches a stable classical (nonbridged) structure in less than 200 fs

Diffractive imaging of dissociation and ground-state dynamics in a complex molecule

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 ultraviolet femtosecond laser pulse to a state characterized by a transition from the iodine 5p⊥ orbital to a mixed 5p ‖ σ hole and CF•2 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 wave packet of the dissociating iodine atom followed by coherent vibrations in the electronic ground state of the C2F4I radical. The radical reaches a stable classical (nonbridged) structure in less than 200 fs

Imaging CF\u3csub\u3e3\u3c/sub\u3eI conical intersection and photodissociation dynamics with ultrafast electron diffraction

Conical intersections play a critical role in excited-state dynamics of polyatomic molecules because they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wave-packet trajectories through these intersections directly. Here, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF3I molecules using ultrafast gas-phase electron diffraction. In the two-photon channel, we have mapped out the real-space trajectories of a coherent nuclear wave packet, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitation of both the umbrella and the breathing vibrational modes in the CF3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab initio nonadiabatic dynamics calculations. Includes supplementary materials. Movie S1 attached below

Imaging the ring opening reaction of 1,3-cyclohexadiene with MeV ultrafast electron diffraction

We resolve the structural dynamics of the ultrafast photoinduced ring opening reaction of 1,3-cyclohexadiene in space and time employing megaelectronvolt gas phase ultrafast electron diffraction. We, furthermore, observe coherent large amplitude motions of the photoproduct