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Papers by Christopher Chantler
Acta Crystallographica Section A Foundations and Advances, 2017
Radiation Physics and Chemistry
Journal of Synchrotron Radiation, 2015
A new approach is introduced for determining X-ray absorption spectroscopy (XAS) spectra on absol... more A new approach is introduced for determining X-ray absorption spectroscopy (XAS) spectra on absolute and relative scales using multiple solutions with different concentrations by the characterization and correction of experimental systematics. This hybrid technique is a development of standard X-ray absorption fine structure (XAFS) along the lines of the high-accuracy X-ray extended range technique (XERT) but with applicability to solutions, dilute systems and cold cell environments. This methodology has been applied to determining absolute XAS of bis(N-n-propyl-salicylaldiminato) nickel(II) and bis(N-i-propyl-salicylaldiminato) nickel(II) complexes with square planar and tetrahedral structures in 15 mMand 1.5 mMdilute solutions. It is demonstrated that transmission XAS from dilute systems can provide excellent X-ray absorption near-edge structure (XANES) and XAFS spectra, and that transmission measurements can provide accurate measurement of subtle differences including coordinatio...
X-Ray Spectrometry, 2003
In line with an ongoing programme to determine accurately x‐ray attenuation coefficients, we have... more In line with an ongoing programme to determine accurately x‐ray attenuation coefficients, we have developed a method for the quantitative determination of the effect on experimental results of monochromator harmonic components in a synchrotron beam. The technique can be adapted to suit a wide variety of experiments, and is of particular interest because it determines the effect of the harmonic components directly. This avoids the necessity for modelling and is therefore robust. Results of a direct determination of the effect of harmonic components illustrate the power of the technique. We extended the technique to quantify the effects of dark current‐induced errors. Copyright © 2003 John Wiley & Sons, Ltd.
Journal of Synchrotron Radiation, 2016
A new theoretical approach and computational package,FDMX, for general calculations of X-ray abso... more A new theoretical approach and computational package,FDMX, for general calculations of X-ray absorption fine structure (XAFS) over an extended energy range within a full-potential model is presented. The final-state photoelectron wavefunction is calculated over an energy-dependent spatial mesh, allowing for a complete representation of all scattering paths. The electronic potentials and corresponding wavefunctions are subject to constraints based on physicality and self-consistency, allowing for accurate absorption cross sections in the near-edge region, while higher-energy results are enabled by the implementation of effective Debye–Waller damping and new implementations of second-order lifetime broadening. These include inelastic photoelectron scattering and, for the first time, plasmon excitation coupling. This is the first full-potential package available that can calculate accurate XAFS spectra across a complete energy range within a single framework and without fitted paramete...
Acta Crystallographica Section A, 2017
Alzheimer’s disease (AD) is a progressive neurodegenerative disorder characterized by the presenc... more Alzheimer’s disease (AD) is a progressive neurodegenerative disorder characterized by the presence of amyloid (Aß) plaques. In addition to modulating senile Aß plaque formation, Aß-Cu complexes are involved in extensive redox chemical reactions. The first protein sequencing studies of the Aβ plaque core (APC) of AD patients identified NH2-terminal heterogeneity and the majority (64%) of the APC-AD Aß peptides begins with a Phe4 residue. This N-truncated sequence produced the highaffinity (dissociation Kd of femtoM ) amino-terminal Cu Ni (ATCUN, H2N-Xaa–Yaa–His) binding motif.
Radiation Physics and Chemistry
ABSTRACT Earlier investigations using the LLNL Spectrometer have revealed several limitations to ... more ABSTRACT Earlier investigations using the LLNL Spectrometer have revealed several limitations to the resolution of observed spectral lines. The first is the broadening due to the finite target source, together with secondary effects due to the bowing of the target. Other limitations relate to the target and spectrometer geometry, and in particular to the small (2R = 30cm) Rowland Circle radius. At small radii the production of a perfect curvature becomes increasingly difficult as distortions of the mosaic spread of crystallite angles are introduced by the stress. This is particularly true of lattice planes with three non-zero Miller indices (e.g., Si111 compared to Si220) and of stiff or thick crystals (e.g., silicon and quartz, which will shatter if greater than 0.2mm crystals are bent to this radius), but small broadening and asymmetrical shifts are also introduced for other crystals. Conversely, soft crystals (such as thin PET) will bend readily to the radius but distort and relax in mountings with fixed bending forces. A set of improvements to the bending techniques for both soft and stiff crystals is addressed. The first and most important development is the use of parallel, vertical posts and (symmetrical) bending points driven by micrometers instead of the earlier formed (i.e., pressed) crystals. The primary advantage is that the curvature from a small number of stress points is calculable, reproducible and does not introduce random stresses and distortions over the surface. The major methods used include the 2-point, 2-bar mount and the 4-point, 4-bar method. Various 4-point, 2-bar methods were also used.
Journal of synchrotron radiation, 2018
Round robin studies have been used across fields of science for quality control testing and to in... more Round robin studies have been used across fields of science for quality control testing and to investigate laboratory dependencies and cross-platform inconsistencies as well as to drive forward the improvement of understanding of experimental systems, systematic effects and theoretical limitations. Here, following the Q2XAFS Workshop and Satellite to IUCr Congress 2017 on `Data Acquisition, Treatment, Storage - quality assurance in XAFS spectroscopy', a mechanism is suggested for a suitable study across XAFS (X-ray absorption fine-structure) beamlines and facilities, to enable each beamline to cross-calibrate, provide representative test data, and to enable collaborative cross-facility activities to be more productive.
Radiation Physics and Chemistry
Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment
Various methods exist to filter cosmic rays from X-ray CCD images with weak X-ray spectra. Distor... more Various methods exist to filter cosmic rays from X-ray CCD images with weak X-ray spectra. Distortions of the characteristics of a spectral profile such as peak centroid and relative integrated peak intensities must be kept to a minimum. Optimum methods are those minimising error bars and widths on the final centroid determination and on relative intensities which remain consistent with
Radiation Physics and Chemistry
Acta Crystallographica Section A Foundations of Crystallography
Acta Crystallographica Section A Foundations of Crystallography
AIP Conference Proceedings, 2003
AIP Conference Proceedings, 2003
The journal of physical chemistry letters, Jan 8, 2016
Recent high-accuracy x-ray absorption measurements of the sandwich organometallics ferrocene (Fc)... more Recent high-accuracy x-ray absorption measurements of the sandwich organometallics ferrocene (Fc) and decamethylferrocene (DmFc) at temperatures close to liquid helium are compared with new full-potential modelling of x-ray absorption fine structure (XAFS) covering the near-edge region (XANES) and above up to k=7/Å. The implementation of optimised calculations of the oscillatory part of the spectrum from the package FDMX allows detailed study of the spectra in regions of the photoelectron momentum most sensitive to differences in the molecular stereochemistry. For Fc and DmFc, this corresponds to the relative rotation of the cyclopentadienyl rings. When applied to high-accuracy XAFS of Fc and DmFc, the FDMX theory gives clear evidence for the eclipsed conformation for Fc and the staggered conformation for DmFc for frozen solutions at circa 15 K. This represents the first clear experimental assignment of the solution structures of Fc and DmFc and reveals the potential of high-accurac...
Acta Crystallographica Section A Foundations and Advances, 2017
Radiation Physics and Chemistry
Journal of Synchrotron Radiation, 2015
A new approach is introduced for determining X-ray absorption spectroscopy (XAS) spectra on absol... more A new approach is introduced for determining X-ray absorption spectroscopy (XAS) spectra on absolute and relative scales using multiple solutions with different concentrations by the characterization and correction of experimental systematics. This hybrid technique is a development of standard X-ray absorption fine structure (XAFS) along the lines of the high-accuracy X-ray extended range technique (XERT) but with applicability to solutions, dilute systems and cold cell environments. This methodology has been applied to determining absolute XAS of bis(N-n-propyl-salicylaldiminato) nickel(II) and bis(N-i-propyl-salicylaldiminato) nickel(II) complexes with square planar and tetrahedral structures in 15 mMand 1.5 mMdilute solutions. It is demonstrated that transmission XAS from dilute systems can provide excellent X-ray absorption near-edge structure (XANES) and XAFS spectra, and that transmission measurements can provide accurate measurement of subtle differences including coordinatio...
X-Ray Spectrometry, 2003
In line with an ongoing programme to determine accurately x‐ray attenuation coefficients, we have... more In line with an ongoing programme to determine accurately x‐ray attenuation coefficients, we have developed a method for the quantitative determination of the effect on experimental results of monochromator harmonic components in a synchrotron beam. The technique can be adapted to suit a wide variety of experiments, and is of particular interest because it determines the effect of the harmonic components directly. This avoids the necessity for modelling and is therefore robust. Results of a direct determination of the effect of harmonic components illustrate the power of the technique. We extended the technique to quantify the effects of dark current‐induced errors. Copyright © 2003 John Wiley & Sons, Ltd.
Journal of Synchrotron Radiation, 2016
A new theoretical approach and computational package,FDMX, for general calculations of X-ray abso... more A new theoretical approach and computational package,FDMX, for general calculations of X-ray absorption fine structure (XAFS) over an extended energy range within a full-potential model is presented. The final-state photoelectron wavefunction is calculated over an energy-dependent spatial mesh, allowing for a complete representation of all scattering paths. The electronic potentials and corresponding wavefunctions are subject to constraints based on physicality and self-consistency, allowing for accurate absorption cross sections in the near-edge region, while higher-energy results are enabled by the implementation of effective Debye–Waller damping and new implementations of second-order lifetime broadening. These include inelastic photoelectron scattering and, for the first time, plasmon excitation coupling. This is the first full-potential package available that can calculate accurate XAFS spectra across a complete energy range within a single framework and without fitted paramete...
Acta Crystallographica Section A, 2017
Alzheimer’s disease (AD) is a progressive neurodegenerative disorder characterized by the presenc... more Alzheimer’s disease (AD) is a progressive neurodegenerative disorder characterized by the presence of amyloid (Aß) plaques. In addition to modulating senile Aß plaque formation, Aß-Cu complexes are involved in extensive redox chemical reactions. The first protein sequencing studies of the Aβ plaque core (APC) of AD patients identified NH2-terminal heterogeneity and the majority (64%) of the APC-AD Aß peptides begins with a Phe4 residue. This N-truncated sequence produced the highaffinity (dissociation Kd of femtoM ) amino-terminal Cu Ni (ATCUN, H2N-Xaa–Yaa–His) binding motif.
Radiation Physics and Chemistry
ABSTRACT Earlier investigations using the LLNL Spectrometer have revealed several limitations to ... more ABSTRACT Earlier investigations using the LLNL Spectrometer have revealed several limitations to the resolution of observed spectral lines. The first is the broadening due to the finite target source, together with secondary effects due to the bowing of the target. Other limitations relate to the target and spectrometer geometry, and in particular to the small (2R = 30cm) Rowland Circle radius. At small radii the production of a perfect curvature becomes increasingly difficult as distortions of the mosaic spread of crystallite angles are introduced by the stress. This is particularly true of lattice planes with three non-zero Miller indices (e.g., Si111 compared to Si220) and of stiff or thick crystals (e.g., silicon and quartz, which will shatter if greater than 0.2mm crystals are bent to this radius), but small broadening and asymmetrical shifts are also introduced for other crystals. Conversely, soft crystals (such as thin PET) will bend readily to the radius but distort and relax in mountings with fixed bending forces. A set of improvements to the bending techniques for both soft and stiff crystals is addressed. The first and most important development is the use of parallel, vertical posts and (symmetrical) bending points driven by micrometers instead of the earlier formed (i.e., pressed) crystals. The primary advantage is that the curvature from a small number of stress points is calculable, reproducible and does not introduce random stresses and distortions over the surface. The major methods used include the 2-point, 2-bar mount and the 4-point, 4-bar method. Various 4-point, 2-bar methods were also used.
Journal of synchrotron radiation, 2018
Round robin studies have been used across fields of science for quality control testing and to in... more Round robin studies have been used across fields of science for quality control testing and to investigate laboratory dependencies and cross-platform inconsistencies as well as to drive forward the improvement of understanding of experimental systems, systematic effects and theoretical limitations. Here, following the Q2XAFS Workshop and Satellite to IUCr Congress 2017 on `Data Acquisition, Treatment, Storage - quality assurance in XAFS spectroscopy', a mechanism is suggested for a suitable study across XAFS (X-ray absorption fine-structure) beamlines and facilities, to enable each beamline to cross-calibrate, provide representative test data, and to enable collaborative cross-facility activities to be more productive.
Radiation Physics and Chemistry
Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment
Various methods exist to filter cosmic rays from X-ray CCD images with weak X-ray spectra. Distor... more Various methods exist to filter cosmic rays from X-ray CCD images with weak X-ray spectra. Distortions of the characteristics of a spectral profile such as peak centroid and relative integrated peak intensities must be kept to a minimum. Optimum methods are those minimising error bars and widths on the final centroid determination and on relative intensities which remain consistent with
Radiation Physics and Chemistry
Acta Crystallographica Section A Foundations of Crystallography
Acta Crystallographica Section A Foundations of Crystallography
AIP Conference Proceedings, 2003
AIP Conference Proceedings, 2003
The journal of physical chemistry letters, Jan 8, 2016
Recent high-accuracy x-ray absorption measurements of the sandwich organometallics ferrocene (Fc)... more Recent high-accuracy x-ray absorption measurements of the sandwich organometallics ferrocene (Fc) and decamethylferrocene (DmFc) at temperatures close to liquid helium are compared with new full-potential modelling of x-ray absorption fine structure (XAFS) covering the near-edge region (XANES) and above up to k=7/Å. The implementation of optimised calculations of the oscillatory part of the spectrum from the package FDMX allows detailed study of the spectra in regions of the photoelectron momentum most sensitive to differences in the molecular stereochemistry. For Fc and DmFc, this corresponds to the relative rotation of the cyclopentadienyl rings. When applied to high-accuracy XAFS of Fc and DmFc, the FDMX theory gives clear evidence for the eclipsed conformation for Fc and the staggered conformation for DmFc for frozen solutions at circa 15 K. This represents the first clear experimental assignment of the solution structures of Fc and DmFc and reveals the potential of high-accurac...