Picosecond X-ray Absorption Spectroscopy of Photochemical Transient Species in Solution

A photoinduced Fe(II) spin crossover reaction in solution is studied with ultrafast x-ray absorption spectroscopy. The iron-nitrogen bond lengthens by 0.21+-0.03 Angstrom in the high-spin transient excited state relative to the ground state

Insulator-to-metal transition induced by mid-IR vibrational excitation in a magnetoresistive manganite

Selective vibrational excitation of insulating Pr0.7Ca0.3MnO3 at 17 ?m triggers a transition to a metallic state. A four order of magnitude drop of the sample resistivity and ultrafast, nanosecond-lived reflectivity changes are observe

Ultrafast gigantic photo-response in (EDO-TTF)2PF6 initiated by 10-fs laser pulses

We photo-exited a charge-ordered organic salt (EDO-TTF)2PF6 with sub-10-fs optical pulses. The photo-induced metallic phase appeared within 80-fs after pumping, characterized by large changes in reflectivity (DELTA R/R~0.8) followed by strong coherent phonon modulatio

HIGH-RESOLUTION SEEDING MONOCHROMATOR DESIGN FOR NGLS *

Abstract A high-resolution soft X-ray monochromator system is designed for self-seeding the next generation FEL sources. It consists of a single variable-line-spacing (VLS) grating, an exit slit, and pre-and collimating mirrors, and operates in the fixed-focus mode to achieve complete tuning of the seeding energy from 200 to 2000 eV with a nearly constant resolving power of greater than 50000, producing transform-limited seed ranging from 1 ps at 200 eV to 100 fs at 2000 eV. The optical delay is of order 1 ps, matching well with that of an electron chicane of moderate magnetic field strength. The design is based on a coherent Gaussian beam treatment of the FEL beam propagating from the upstream SASE undulator through the entire seeding monochromator system, preserving the transverse beam profile entering the downstream seeding undulator to ensure maximum coupling efficiency with the reentrant electron beam

Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance

Ultrafast time-resolved studies of photocatalytic thin films can provide a wealth of information crucial for understanding and thereby improving the performance of these materials by directly probing electronic structure, reaction intermediates, and charge carrier dynamics. The interpretation of transient spectra, however, can be complicated by thermally induced structural distortions, which appear within the first few picoseconds following excitation due to carrier–phonon scattering. Here we present a comparison of ex situ steady-state thermal difference spectra and transient absorption spectra spanning from NIR to hard X-ray energies of hematite thin films grown by atomic layer deposition. We find that beyond the first 100 picoseconds, the transient spectra measured for all excitation wavelengths and probe energies are almost entirely due to thermal effects as the lattice expands in response to the ultrafast temperature jump and then cools to room temperature on the microsecond timescale. At earlier times, a broad excited state absorption band that is assigned to free carriers appears at 675 nm, and the lifetime and shape of this feature also appear to be mostly independent of excitation wavelength. The combined spectroscopic data, which are modeled with density functional theory and full multiple scattering calculations, support an assignment of the optical absorption spectrum of hematite that involves two LMCT bands that nearly span the visible spectrum. Our results also suggest a framework for shifting the ligand-to-metal charge transfer absorption bands of ferric oxide films from the near-UV further into the visible part of the solar spectrum to improve solar conversion efficiency

Scientific Opportunities with an X-ray Free-Electron Laser Oscillator

An X-ray free-electron laser oscillator (XFELO) is a new type of hard X-ray source that would produce fully coherent pulses with meV bandwidth and stable intensity. The XFELO complements existing sources based on self-amplified spontaneous emission (SASE) from high-gain X-ray free-electron lasers (XFEL) that produce ultra-short pulses with broad-band chaotic spectra. This report is based on discussions of scientific opportunities enabled by an XFELO during a workshop held at SLAC on June 29 - July 1, 2016Comment: 21 pages, 12 figure

Probing the hydrogen-bond network of water via time-resolved soft x-ray spectroscopy

We report time-resolved studies of hydrogen bonding in liquid H2O, in response to direct excitation of the O-H stretch mode at 3 mu m, probed via soft x-ray absorption spectroscopy at the oxygen K-edge. This approach employs a newly developed nanofluidic cell for transient soft x-ray spectroscopy in liquid phase. Distinct changes in the near-edge spectral region (XANES) are observed, and are indicative of a transient temperature rise of 10K following transient laser excitation and rapid thermalization of vibrational energy. The rapid heating occurs at constant volume and the associated increase in internal pressure, estimated to be 8MPa, is manifest by distinct spectral changes that differ from those induced by temperature alone. We conclude that the near-edge spectral shape of the oxygen K-edge is a sensitive probe of internal pressure, opening new possibilities for testing the validity of water models and providing new insight into the nature of hydrogen bonding in water

Cannibalism, cell survival, and endocrine resistance in breast cancer

Breast cancer cells often respond to an endocrine therapy by altering expression of specific estrogen-responsive genes and inducing autophagy, a cannibalistic lysosomal pathway. Autophagy eliminates damaged or other organelles, allowing the recovery of the energy stored in their macromolecules to attempt restoration of metabolic homeostasis. Induction of autophagy can result from activation of the unfolded protein response following metabolic stress, the final cell fate often being determined by the extent and duration of autophagy. A study by Gonzalez-Malerva and colleagues builds upon this extensive knowledge, adding HSPB8 to the list of altered genes associated with endocrine resistance in breast cancer and describing the ability of HSPB8 to regulate autophagy and confer tamoxifen resistance