Session A12: Advances in Real-Time Measurement of Structural Transformations

Tabletop Extreme Ultraviolet Spectroscopy of Element-Specific Organometallic Photophysics

High-harmonic extreme ultraviolet (XUV) spectroscopy has the potential to provide the elemental, oxidation-state, and spin-state specificity of core-level spectroscopy with the convenience and ultrafast time resolution of tabletop laser sources. We will show that M-edge spectroscopy of first-row transition metal complexes (3p$\to $3d excitation) is a sensitive probe of the electronic structure of organometallic complexes in solution. Furthermore, this technique can be used to determine the relaxation dynamics of these molecules in the first few femtoseconds to nanoseconds after photoexcitation.   

Advancing the molecular movie: Femtosecond X-ray scattering of an electrocyclic chemical reaction

Since it began operation in 2009, SLAC's Linac Coherent Light Source (LCLS) has allowed scientists to make new types of X-ray measurements that were once thought unattainable by delivering one trillion X-ray photons in incredibly short bursts of less than a few femtoseconds. It was promised that this astonishing quantity of photons, delivered in such a small slice of time, could capture the motions of atoms in chemical reactions. Now we have used this capability to make a ``molecular movie'' of a molecule undergoing a chemical reaction from start to finish, with frames just a few femtoseconds long. We assembled the movie by taking individual X-ray snapshots of the molecules that show the positions of their atoms at each moment in time. Comparing these results to computer simulations of the reaction, we determined the routes the individual molecules followed as it's structure rearranged. This is the first step in developing robust methods for visualizing molecular motions in chemistry, biology, and materials science at the atomic scale. Please enjoy the movie!   

Structure and Dynamics with Ultrafast Electron Microscopes

In this talk I will describe how combining ultrafast lasers and electron microscopes in novel ways makes it possible to directly `watch' the time-evolving structure of condensed matter, both at the level of atomic-scale structural rearrangements in the unit cell and at the level of a material's nano- microstructure. First, I will briefly describe my group's efforts to develop ultrafast electron diffraction using radio- frequency compressed electron pulses in the 100keV range, a system that rivals the capabilities of xray free electron lasers for diffraction experiments. I will give several examples of the new kinds of information that can be gleaned from such experiments. In vanadium dioxide we have mapped the detailed reorganization of the unit cell during the much debated insulator-metal transition. In particular, we have been able to identify and separate lattice structural changes from valence charge density redistribution in the material on the ultrafast timescale. In doing so we uncovered a previously unreported optically accessible phase/state of vanadium dioxide that has monoclinic crystallography like the insulator, but electronic structure and properties that are more like the rutile metal. We have also combined these dynamic structural measurements with broadband ultrafast spectroscopy to make detailed connections between structure and properties for the photoinduced insulator to metal transition. Second, I will show how dynamic transmission electron microscopy (DTEM) can be used to make direct, real space images of nano-microstructural evolution during laser-induced crystallization of amorphous semiconductors at unprecedented spatio-temporal resolution. This is a remarkably complex process that involves several distinct modes of crystal growth and the development of intricate microstructural patterns on the nanosecond to ten microsecond timescales all of which can be imaged directly with DTEM.   

Understanding subcellular function on the nanometer scale in real time: Single-molecule imaging in living bacteria

It has long been recognized that microorganisms play a central role in our lives. By beating the diffraction limit that restricts traditional light microscopy, single-molecule fluorescence imaging is a precise, noninvasive way to sensitively probe position and dynamics, even in living cells. We are pioneering this super-resolution imaging method for unraveling important biological processes in live bacteria, and I will discuss how we infer function from subcellular dynamics (Tuson and Biteen, Analytical Chemistry 2015). In particular, we have understood the mechanism of membrane-bound transcription regulation in the pathogenic \textit{Vibrio cholerae}, revealed an intimate and dynamic coupling between DNA mismatch recognition and DNA replication, and measured starch utilization in an important member of the human gut microbiome.   

Orbital-specific mapping of chemical dynamics with ultrafast x-rays

Charge and spin density changes at the metal sites of transition-metal complexes and in metalloproteins determine reactivity and selectivity. To understand their function and to optimize complexes for photocatalytic applications the changes of charge and spin densities need to be mapped and ultimately controlled. I will discuss how time-resolved soft x-ray spectroscopy enables a fundamental understanding of local atomic and intermolecular interactions and their dynamics on atomic length and time scales of {\AA}ngstr\"{o}ms and femtoseconds. The approach consists in using time-resolved, atom- and orbital-specific x-ray spectroscopy and quantum chemical theory to map the frontier-orbital interactions and their evolution in real time of ultrafast chemical transformations. We recently used femtosecond resonant inelastic x-ray scattering (RIXS, the x-ray analog of resonant Raman scattering) at the x-ray free-electron laser LINAC Coherent Light Source (LCLS, Stanford, USA) to probe the reaction dynamics of a transition-metal complex in solution on the femtosecond time scale. Spin crossover and ligation are found to define the excited-state dynamics. It is demonstrated how correlating orbital symmetry and orbital interactions with spin multiplicity allows for determining the reactivity of short-lived reaction intermediates. I will discuss how this complements approaches that probe structural dynamics and how it can be extended to map the local chemical interactions and their dynamical evolution in metalloproteins.