88 research outputs found
Rate equations for nitrogen molecules in ultrashort and intense x-ray pulses
We study theoretically the quantum dynamics of nitrogen molecules (N2) exposed to intense and ultrafast x-rays at a wavelength of 1.1 nm (1100eV photon energy) from the Linac Coherent Light Source (LCLS) free electron laser. Molecular rate equations are derived to describe the intertwined photoionization, decay, and dissociation processes occurring for N2. This model complements our earlier phenomenological approaches, the single-atom, symmetric-sharing, and fragmentation-matrix models of 2012 (J. Chem. Phys. 136 214310). Our rate-equations are used to obtain the effective pulse energy at the sample and the time scale for the dissociation of the metastable dication . This leads to a very good agreement between the theoretically and experimentally determined ion yields and, consequently, the average charge states. The effective pulse energy is found to decrease with shortening pulse duration. This variation together with a change in the molecular fragmentation pattern and frustrated absorption - an effect that reduces absorption of x-rays due to (double) core hole formation - are the causes for the drop of the average charge state with shortening LCLS pulse duration discovered previously
Ultrafast absorption of intense x rays by nitrogen molecules
We devise a theoretical description for the response of nitrogen molecules
(N2) to ultrashort and intense x rays from the free electron laser (FEL) Linac
Coherent Light Source (LCLS). We set out from a rate-equation description for
the x-ray absorption by a nitrogen atom. The equations are formulated using all
one-x-ray-photon absorption cross sections and the Auger and radiative decay
widths of multiply-ionized nitrogen atoms. Cross sections are obtained with a
one-electron theory and decay widths are determined from ab initio computations
using the Dirac-Hartree-Slater (DHS) method. We also calculate all binding and
transition energies of nitrogen atoms in all charge states with the DHS method
as the difference of two self-consistent field calculations (Delta SCF method).
To describe the interaction with N2, a detailed investigation of intense
x-ray-induced ionization and molecular fragmentation are carried out. As a
figure of merit, we calculate ion yields and the average charge state measured
in recent experiments at the LCLS. We use a series of phenomenological models
of increasing sophistication to unravel the mechanisms of the interaction of x
rays with N2: a single atom, a symmetric-sharing model, and a
fragmentation-matrix model are developed. The role of the formation and decay
of single and double core holes, the metastable states of N_2^2+, and molecular
fragmentation are explained.Comment: 16 pages, 6 figures, 2 tables, RevTeX4.1, supporting materials in the
Data Conservancy, revise
Critical slowing of the spin and charge density wave order in thin film Cr following photoexcitation
We report on the evolution of the charge density wave (CDW) and spin density
wave (SDW) order of a chromium film following photoexcitation with an ultrafast
optical laser pulse. The CDW is measured by ultrafast time-resolved x-ray
diffraction of the CDW satellite that tracks the suppression and recovery of
the CDW following photoexcitation. We find that as the temperature of the film
approaches a discontinuous phase transition in the CDW and SDW order, the time
scales of recovery increase exponentially from the expected thermal time
scales. We extend a Landau model for SDW systems to account for this critical
slowing with the appropriate boundary conditions imposed by the geometry of the
thin film system. This model allows us to assess the energy barrier between
available CDW/SDW states with different spatial periodicities.Comment: Author typo fixe
Ultrafast Structural Dynamics along the β − γ Phase Transition Path in MnAs
International audienceWe investigate the orthorhombic distortion and the structural dynamics of epitaxial MnAs layers on GaAs(001) using static and time-resolved x-ray diffraction. Laser-induced intensity oscillations of Bragg reflections allow us to identify the optical phonon associated with orthorhombic distortion and to follow its softening along the path towards an undistorted phase of hexagonal symmetry. The frequency of this mode falls in the THz range, in agreement with recent calculations. Incomplete softening suggests that the transformation deviates from a purely second-order displacive transition
Metalloprotein entatic control of ligand-metal bonds quantified by ultrafast x-ray spectroscopy
The multifunctional protein cytochrome c (cyt c) plays key roles in electron transport and apoptosis, switching function by modulating bonding between a heme iron and the sulfur in a methionine residue. This Fe-S(Met) bond is too weak to persist in the absence of protein constraints. We ruptured the bond in ferrous cyt c using an optical laser pulse and monitored the bond reformation within the protein active site using ultrafast x-ray pulses from an x-ray free-electron laser, determining that the Fe-S(Met) bond enthalpy is ~4 kcal/mol stronger than in the absence of protein constraints. The 4 kcal/mol is comparable with calculations of stabilization effects in other systems, demonstrating how biological systems use an entatic state for modest yet accessible energetics to modulate chemical function
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