New Developments in Charge Transfer Multiplet Calculations: Projection Operations, Mixed-Spin States and pi-Bonding

This paper presents a number of new additions to the charge transfer multiplet calculations as used in the calculation of L edge X-ray absorption spectra of 3d and 4d transition metal systems, both oxides and coordination compounds. The focus of the paper is on the consequences of the optimized spectral simulations for the ground state, where we make use of a recently developed projection technique. This method is also used to develop the concept of a mixed-spin ground state, i.e. a state that is a mixture of a high-spin and low-spin state due to spin-orbit coupling combined with strong covalency. The charge transfer mechanism to describe {pi}-bonding uses the mixing of the metal-to-ligand charge transfer (MLCT) channel in addition to the normal CT channel and allows for the accurate simulation of {pi}-bonding systems, for example cyanides

THz Pump and X-Ray Probe Development at LCLS

We report on measurements of broadband, intense, coherent transition radiation at terahertz frequencies, generated as the highly compressed electron bunches in Linear Coherent Light Source (LCLS) pass through a thin metal foil. The foil is inserted at 45{sup o} to the electron beam, 31 m downstream of the undulator. The THz emission passes downward through a diamond window to an optical table below the beamline. A fully compressed 350-pC bunch produces up to 0.5 mJ in a nearly half-cycle pulse of 50 fs FWHM with a spectrum peaking at 10 THz. We estimate a peak field at the focus of over 2.5 GV/m. A 20-fs Ti:sapphire laser oscillator has recently been installed for electro-optic measurements. We are developing plans to add an x-ray probe to this THz pump, by diffracting FEL x rays onto the table with a thin silicon crystal. The x rays would arrive with an adjustable time delay after the THz. This will provide a rapid start to user studies of materials excited by intense single-cycle pulses and will serve as a step toward a THz transport line for LCLS-II

Sulfur K-Edge XAS and DFT Calculations on [Fe4S4]2+Clusters: Effects of H-bonding and Structural Distortion on Covalency and SpinTopology

Sulfur K-edge X-ray absorption spectroscopy of a hydrogen-bonded elongated [Fe{sub 4}S{sub 4}]{sup 2+} cube is reported. The data show that this synthetic cube is less covalent than a normal compressed cube with no hydrogen bonding. DFT calculations reveal that the observed difference in electronic structure has significant contributions from both the cluster distortion and from hydrogen bonding. The elongated and compressed Fe{sub 4}S{sub 4} structures are found to have different spin topologies (i.e., orientation of the delocalized Fe{sub 2}S{sub 2} subclusters which are antiferromagnetically coupled to each other). It is suggested that the H-bonding interaction with the counterion does not contribute to the cluster elongation. A magneto-structural correlation is developed for the Fe{sub 4}S{sub 4} cube that is used to identify the redoxactive Fe{sub 2}S{sub 2} subclusters in active sites of HiPIP and ferredoxin proteins involving these clusters

Bulk Superconductivity and Disorder in Single Crystals of LaFePO

We have studied the intrinsic normal and superconducting properties of the oxypnictide LaFePO. These samples exhibit bulk superconductivity and the evidence suggests that stoichiometric LaFePO is indeed superconducting, in contrast to other reports. We find that superconductivity is independent of the interplane residual resistivity {rho}{sub 0} and discuss the implications of this on the nature of the superconducting order parameter. Finally we find that, unlike T{sub c}, other properties in single-crystal LaFePO including the resistivity and magnetoresistance, can be very sensitive to disorder

Intense terahertz pulses from SLAC electron beams using coherent transition radiation

SLAC has two electron accelerators, the Linac Coherent Light Source (LCLS) and the Facility for Advanced Accelerator Experimental Tests (FACET), providing high-charge, high peak-current, femtosecond electron bunches. These characteristics are ideal for generating intense broadband terahertz (THz) pulses via coherent transition radiation. For LCLS and FACET respectively, the THz pulse duration is typically 20 and 80 fs RMS and can be tuned via the electron bunch duration; emission spectra span 3-30 THz and 0.5 THz-5 THz; and the energy in a quasi-half-cycle THz pulse is 0.2 and 0.6 mJ. The peak electric field at a THz focus has reached 4.4 GV/m (0.44 V/Å) at LCLS. This paper presents measurements of the terahertz pulses and preliminary observations of nonlinear materials response

Sulfur K-Edge XAS and DFT Calculations on P450 Model Complexes: Effects of Hydrogen Bonding on Electronic Structure and Redox Potentials

Abstract: Hydrogen bonding (H-bonding) is generally thought to play an important role in tuning the electronic structure and reactivity of metal-sulfur sites in proteins. To develop a quantitative understanding of this effect, S K-edge X-ray absorption spectroscopy (XAS) has been employed to directly probe ligandmetal bond covalency, where it has been found that protein active sites are significantly less covalent than their related model complexes. Sulfur K-edge XAS data are reported here on a series of P450 model complexes with increasing H-bonding to the ligated thiolate from its substituent. The XAS spectroscopic results show a dramatic decrease in preedge intensity. DFT calculations reproduce these effects and show that the observed changes are in fact solely due to H-bonding and not from the inductive effect of the substituent on the thiolate. These calculations also indicate that the H-bonding interaction in these systems is mainly dipolar in nature. The-2.5 kcal/mol energy of the H-bonding interaction was small relative to the large change in ligand-metal bond covalency (30%) observed in the data. A bond decomposition analysis of the total energy is developed to correlate the preedge intensity change to the change in Fe-S bonding interaction on H-bonding. This effect is greater for the reduced than the oxidized state, leading to a 260 mV increase in the redox potential. A simple model shows that E ° should vary approximately linearly with the covalency of the Fe-S bond in the oxidized state, which can be determined directly from S K-edge XAS

X-ray Absorption Spectroscopy and Density Functional Theory Studies of [(H3buea)FeIII-X]n1 (X= S2-, O2-,OH-): Comparison of Bonding and Hydrogen Bonding in Oxo and Sulfido Complexes

Iron L-edge, iron K-edge, and sulfur K-edge X-ray absorption spectroscopy was performed on a series of compounds [Fe{sup III}H{sub 3}buea(X)]{sup n-} (X = S{sup 2-}, O{sup 2-}, OH{sup -}). The experimentally determined electronic structures were used to correlate to density functional theory calculations. Calculations supported by the data were then used to compare the metal-ligand bonding and to evaluate the effects of H-bonding in Fe{sup III}-O vs Fe{sup III-}S complexes. It was found that the Fe{sup III-}O bond, while less covalent, is stronger than the FeIII-S bond. This dominantly reflects the larger ionic contribution to the Fe{sup III-}O bond. The H-bonding energy (for three H-bonds) was estimated to be -25 kcal/mol for the oxo as compared to -12 kcal/mol for the sulfide ligand. This difference is attributed to the larger charge density on the oxo ligand resulting from the lower covalency of the Fe-O bond. These results were extended to consider an Fe{sup IV-}O complex with the same ligand environment. It was found that hydrogen bonding to Fe{sup IV-}O is less energetically favorable than that to Fe{sup III-}O, which reflects the highly covalent nature of the Fe{sup IV-}O bond