Femtosecond-Terawatt Hard X Ray Pulse Generation with Chirped Pulse Amplification on a Free Electron Laser

Advances of high intensity lasers have opened up the field of strong field physics and led to a broad range of technological applications. Recent x ray laser sources and optics development makes it possible to obtain extremely high intensity and brightness at x ray wavelengths. In this paper, we present a system design that implements chirped pulse amplification for hard x ray free electron lasers. Numerical modeling with realistic experimental parameters show that near-transform-limit single-femtosecond hard x ray laser pulses with peak power exceeding 1 TW and brightness exceeding $4\times10^{35}~$s$^{-1}$mm$^{-2}$mrad$^{-2}$0.1\%bandwdith$^{-1}$ can be consistently generated. Realization of such beam qualities is essential for establishing systematic and quantitative understanding of strong field x-ray physics and nonlinear x ray optics phenomena.Comment: 23 pages, 7 figures, Accepted by PR

Imaging ultrafast excited state pathways in transition metal complexes by X-ray transient absorption and scattering using X-ray free electron laser source

This report will describe our recent studies of transition metal complex structural dynamics on the fs and ps time scales using an X-ray free electron laser source, Linac Coherent Light Source (LCLS). Ultrafast XANES spectra at the Ni K-edge of nickel(II) tetramesitylporphyrin (NiTMP) were successfully measured for optically excited state at a timescale from 100 fs to 50 ps, providing insight into its sub-ps electronic and structural relaxation processes. Importantly, a transient reduced state Ni(I) (π, 3d(x2−y2)) electronic state is captured through the interpretation of a short-lived excited state absorption on the low-energy shoulder of the edge, which is aided by the computation of X-ray transitions for postulated excited electronic states. The observed and computed inner shell to valence orbital transition energies demonstrate and quantify the influence of electronic configuration on specific metal orbital energies. A strong influence of the valence orbital occupation on the inner shell orbital energies indicates that one should not use the transition energy from 1s to other orbitals to draw conclusions about the d-orbital energies. For photocatalysis, a transient electronic configuration could influence d-orbital energies up to a few eV and any attempt to steer the reaction pathway should account for this to ensure that external energies can be used optimally in driving desirable processes. NiTMP structural evolution and the influence of the porphyrin macrocycle conformation on relaxation kinetics can be likewise inferred from this study

Determination of nonthermal bonding origin of a novel photoexcited lattice instability in SnSe

Interatomic forces that bind materials are largely determined by an often complex interplay between the electronic band-structure and the atomic arrangements to form its equilibrium structure and dynamics. As these forces also determine the phonon dispersion, lattice dynamics measurements are often crucial tools for understanding how materials transform between different structures. This is the case for the mono-chalcogenides which feature a number of lattice instabilities associated with their network of resonant bonds and a large tunability in their functional properties. SnSe hosts a novel lattice instability upon above-bandgap photoexcitation that is distinct from the distortions associated with its high temperature phase transition, demonstrating that photoexcitation can alter the interatomic forces significantly different than thermal excitation. Here we report decisive time-resolved X-ray scattering-based measurements of the nonequlibrium lattice dynamics in SnSe. By fitting interatomic force models to the excited-state dispersion, we determine this instability as being primarily due to changes in the fourth-nearest neighbor bonds that connect bilayers, with relatively little change to the intralayer resonant bonds. In addition to providing critical insight into the nonthermal bonding origin of the instability in SnSe, such measurements will be crucial for understanding and controlling materials properties under non-equilibrium conditions

Ultrafast Excited State Relaxation of a Metalloporphyrin Revealed by Femtosecond X-ray Absorption Spectroscopy

Photoexcited Nickel­(II) tetramesitylporphyrin (NiTMP), like many open-shell metalloporphyrins, relaxes rapidly through multiple electronic states following an initial porphyrin-based excitation, some involving metal centered electronic configuration changes that could be harnessed catalytically before excited state relaxation. While a NiTMP excited state present at 100 ps was previously identified by X-ray transient absorption (XTA) spectroscopy at a synchrotron source as a relaxed (d,d) state, the lowest energy excited state (<i>J. Am. Chem. Soc.</i>, <b>2007</b>, <i>129</i>, 9616 and <i>Chem. Sci.</i>, <b>2010</b>, <i>1</i>, 642), structural dynamics before thermalization were not resolved due to the ∼100 ps duration of the available X-ray probe pulse. Using the femtosecond (fs) X-ray pulses of the Linac Coherent Light Source (LCLS), the Ni center electronic configuration from the initial excited state to the relaxed (d,d) state has been obtained via ultrafast Ni K-edge XANES (X-ray absorption near edge structure) on a time scale from hundreds of femtoseconds to 100 ps. This enabled the identification of a short-lived Ni­(I) species aided by time-dependent density functional theory (TDDFT) methods. Computed electronic and nuclear structure for critical excited electronic states in the relaxation pathway characterize the dependence of the complex’s geometry on the electron occupation of the 3d orbitals. Calculated XANES transitions for these excited states assign a short-lived transient signal to the spectroscopic signature of the Ni­(I) species, resulting from intramolecular charge transfer on a time scale that has eluded previous synchrotron studies. These combined results enable us to examine the excited state structural dynamics of NiTMP prior to thermal relaxation and to capture intermediates of potential photocatalytic significance