A "circularisation" method to repair deformations and determine the centre of velocity map images

A problem besetting the analysis of velocity map images, particularly those of photoelectrons, is the presence of distortions that cause the features in the image to deviate from circularity, leading to a loss of resolution in the spectrum extracted. A method is presented to repair such distortions based on fitting the angular behaviour of each of the ring structures to a trigonometric expansion. The repair function allows the intensity at any value of radius and angle to be mapped to a new position that removes the distortion and returns the features to circular. While the method relies on the analysis of the structure in an image, it could also be applied to determine the “repair function” using a calibration image (or series of images) for the experiment. Once the image has been circularised it can be processed by any of the approaches that have been developed for that purpose. The analysis also enables the image centre to be determined with high accuracy. The fitting method utilises an inverse Abel transformation of the image in polar coordinates as a means to reshape the image into a series of spectral features in order to determine the radial position of features at each angle. Although the velocity distribution is not in general spherically symmetric and so this is not a mathematically correct means to extract the velocity distribution, the feature positions are accurately reproduced in the resulting spectrum while the intensity and anisotropy parameters can be remarkably close to those obtained using the proper inverse Abel transformation of the imageS.T.G. acknowledges support by the Australian Research Council Discovery Project Grant No. DP160102585

Vibronic coupling in the superoxide anion: The vibrational dependence of the photoelectron angular distribution

We present a comprehensive photoelectron imaging study of the O₂(X³Σg⁻,v′=0–6)←O₂⁻(X²Πg,v′′=0) and O₂(a¹Δg,v′=0–4)←O₂⁻(X²Πg,v′′=0)photodetachment bands at wavelengths between 900 and 455 nm, examining the effect of vibronic coupling on the photoelectron angular distribution (PAD). This work extends the v′=1–4 data for detachment into the ground electronic state, presented in a recent communication [R. Mabbs, F. Mbaiwa, J. Wei, M. Van Duzor, S. T. Gibson, S. J. Cavanagh, and B. R. Lewis, Phys. Rev. A82, 011401–R (2010)]. Measured vibronic intensities are compared to Franck–Condon predictions and used as supporting evidence of vibronic coupling. The results are analyzed within the context of the one-electron, zero core contribution (ZCC) model [R. M. Stehman and S. B. Woo, Phys. Rev. A23, 2866 (1981)]. For both bands, the photoelectron anisotropy parameter variation with electron kinetic energy,β(E), displays the characteristics of photodetachment from a d-like orbital, consistent with the π∗g 2p highest occupied molecular orbital of O₂⁻. However, differences exist between the β(E) trends for detachment into different vibrational levels of the X³Σg⁻ and a ¹Δg electronic states of O₂. The ZCC model invokes vibrational channel specific “detachment orbitals” and attributes this behavior to coupling of the electronic and nuclear motion in the parent anion. The spatial extent of the model detachment orbital is dependent on the final state of O₂: the higher the neutral vibrational excitation, the larger the electron binding energy. Although vibronic coupling is ignored in most theoretical treatments of PADs in the direct photodetachment of molecular anions, the present findings clearly show that it can be important. These results represent a benchmark data set for a relatively simple system, upon which to base rigorous tests of more sophisticated models.The authors gratefully acknowledge support by the National Science Foundation Grant No. CHE-0748738 and ANU ARC Discovery Projects under Grant Nos. DP0666267 and DP0880850

A Review of the Classification of Opal with Reference to Recent New Localities

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).Our examination of over 230 worldwide opal samples shows that X-ray diffraction (XRD) remains the best primary method for delineation and classification of opal-A, opal-CT and opal-C, though we found that mid-range infra-red spectroscopy provides an acceptable alternative. Raman, infra-red and nuclear magnetic resonance spectroscopy may also provide additional information to assist in classification and provenance. The corpus of results indicated that the opal-CT group covers a range of structural states and will benefit from further multi-technique analysis. At the one end are the opal-CTs that provide a simple XRD pattern (“simple” opal-CT) that includes Ethiopian play-of-colour samples, which are not opal-A. At the other end of the range are those opal-CTs that give a complex XRD pattern (“complex” opal-CT). The majority of opal-CT samples fall at this end of the range, though some show play-of-colour. Raman spectra provide some correlation. Specimens from new opal finds were examined. Those from Ethiopia, Kazakhstan, Madagascar, Peru, Tanzania and Turkey all proved to be opal-CT. Of the three specimens examined from Indonesian localities, one proved to be opal-A, while a second sample and the play-of-colour opal from West Java was a “simple” Opal-CT. Evidence for two transitional types having characteristics of opal-A and opal-CT, and “simple” opal-CT and opal-C are presented

Pervasive interactions between methyl torsion and low frequency vibrations in S-0 and S-1 p-fluorotoluene

We report two dimensional laser induced fluorescence spectral images exploring the lower torsion-vibration manifolds in S0 (E < 560 cm−1) and S1 (E < 420 cm−1) p-fluorotoluene. Analysis of the images reveals strong torsion-vibration interactions and provides an extensive set of torsion-vibration state energies in both electronic states (estimated uncertainty ±0.2 cm−1), which are fit to determine key constants including barrier heights, torsional constants, and torsion-vibration interaction constants. The dominant interactions in both electronic states are between methyl torsion (internal rotation) and the lowest frequency out-of-plane modes, D20 and D19, both of which involve a methyl wagging motion. This is the second aromatic (following toluene) for which a significant interaction between torsion and methyl out-of-plane wagging vibrations has been quantified. Given the generic nature of this motion in substituted toluenes and similar molecules, this mechanism for torsion-vibration coupling may be common in these types of molecules. The inclusion of torsion-vibration coupling affects key molecular constants such as barrier heights and torsional (and rotational) constants, and the possibility of such an interaction should thus be considered in spectral analyses when determining parameters in these types of molecules. p-Fluorotoluene is the first molecule in which the role of methyl torsion in promoting intramolecular vibrational energy redistribution (IVR) was established and the observed torsion-vibration coupling provides one conduit for the state mixing that is a precursor to IVR, as originally proposed by Moss et al. [J. Chem. Phys. 86, 51 (1987)].We thank the staff of the Technical Services Unit for their input into the construction and maintenance of the experimental apparatus. We thank Professor Timothy Wright, Dr. Adrian Gardner, and Mr. William Tuttle for fruitful exchanges concerning the spectroscopy of pFT and for providing a copy of their pFT REMPI spectrum. L.D.S. thanks the Australian Government for the award of a Ph.D. scholarship

Simulating the Feasibility of Using Liquid Micro-Jets for Determining Electron–Liquid Scattering Cross-Sections

The extraction of electron–liquid phase cross-sections (surface and bulk) is proposed through the measurement of (differential) energy loss spectra for electrons scattered from a liquid micro-jet. The signature physical elements of the scattering processes on the energy loss spectra are highlighted using a Monte Carlo simulation technique, originally developed for simulating electron transport in liquids. Machine learning techniques are applied to the simulated electron energy loss spectra, to invert the data and extract the cross-sections. The extraction of the elastic cross-section for neon was determined within 9% accuracy over the energy range 1–100 eV. The extension toward the simultaneous determination of elastic and ionisation cross-sections resulted in a decrease in accuracy, now to within 18% accuracy for elastic scattering and 1% for ionisation. Additional methods are explored to enhance the accuracy of the simultaneous extraction of liquid phase cross-sections

Vibronic coupling in the superoxide anion: the vibrational dependence of the photoelectron angular distribution

We present a comprehensive photoelectron imaging study of the O2(X 3Σg−,v′ = 0–6)←O2−(X 2Πg,v″ = 0) and O2(a 1Δg,v′ = 0–4)←O2−(X 2Πg,v″ = 0) photodetachment bands at wavelengths between 900 and 455 nm, examining the effect of vibronic coupling on the photoelectron angular distribution (PAD). This work extends the v′ = 1–4 data for detachment into the ground electronic state, presented in a recent communication. Measured vibronic intensities are compared to Franck–Condon predictions and used as supporting evidence of vibronic coupling. The results are analyzed within the context of the one-electron, zero core contribution (ZCC) model. For both bands, the photoelectron anisotropy parameter variation with electron kinetic energy, β(E), displays the characteristics of photodetachment from a d-like orbital, consistent with the πg∗ 2p highest occupied molecular orbital of O2−. However, differences exist between the β(E) trends for detachment into different vibrational levels of the X 3Σg− and a 1Δg electronic states of O2. The ZCC model invokes vibrational channel specific “detachment orbitals” and attributes this behavior to coupling of the electronic and nuclear motion in the parent anion. The spatial extent of the model detachment orbital is dependent on the final state of O2: the higher the neutral vibrational excitation, the larger the electron binding energy. Although vibronic coupling is ignored in most theoretical treatments of PADs in the direct photodetachment of molecular anions, the present findings clearly show that it can be important. These results represent a benchmark data set for a relatively simple system, upon which to base rigorous tests of more sophisticated models

A direct comparison of vibrational deactivation of hexafluorobenzene excited by infrared multiple photon absorption and internal conversion

We report the first direct comparison between energy transfer parameters measured using infrared multiphoton absorption (IRMPA) versus ultraviolet (UV) excitation followed by rapid internal conversion (IC). Highly excited hexafluorobenzene (HFB) molecules in the electronic ground state were prepared by (i) IRMPA by CO2 laser pumping to an average initial energy of 14500-17500cm-1 and (ii) UV excitation to ∼40300cm-1 followed by IC. The vibrational deactivation of the highly excited HFB by the monatomic collider gas argon was monitored by time-resolved infrared fluorescence. The results for the two methods are identical within experimental error, demonstrating the viability of IRMPA as a method of state preparation for vibrational deactivation experiments involving large molecules. © 1998 American Institute of Physics

Photodissociation dynamics of the HCNN radical

The photodissociation dynamics of the diazomethyl (HCNN) radical have been studied using fast radical beam photofragment translational spectroscopy. A photofragment yield spectrum was obtained for the range of 25 510-40 820 cm-1, and photodissociation was shown to occur for energies above 25 600 cm-1. The only product channel observed was the formation of CH and N2. Fragment translational energy and angular distributions were obtained at several energies in the range covered by the photofragment yield spectrum. The fragment translational energy distributions showed at least two distinct features at energies up to 4.59 eV, and were not well fit by phase space theory at any of the excitation energies studied. A revised C-N bond dissociation energy and heat of formation for HCNN, D0 (HC-NN) =1.139±0.019 eV and Δf H0 (HCNN) =5.010±0.023 eV, were determined. © 2006 American Institute of Physics.Ann Elise Faulhaber, Jason R. Gascooke, Alexandra A. Hoops, and Daniel M. Neumar