RESUMEN
High-resolution velocity-map imaged photoelectron spectra of the ethynyl anions C2H- and C2D- are measured at photon wavelengths between 355 and 266 nm to investigate the complex interactions between the closely lying XÌ2Σ+ and Ã2Π electronic states. An indicative kinetic energy resolution of 0.4%, together with the full angular dependence of the fast electrons, provides a detailed description of the vibronically coupled structure. It is demonstrated that a modest quadratic vibronic coupling model, parameterized by the quasidiabatic ansatz, is sufficient to accurately recreate all the observed vibronic interactions. Simulated spectra are shown to be in excellent agreement with the experimental data, verifying the proposed model and providing a framework that may be used to accurately simulate spectra of larger C2nH monohydride carbon chains. New spectral assignments are supported by experimental electron anisotropy measurements and Dyson orbital calculations.
RESUMEN
Weakly bound anionic systems present a new domain for negative ion spectroscopy. Here we report on a multifaceted study of the CH2CN- dipole-bound state, employing high-resolution photoelectron spectroscopy from 130 different wavelengths, velocity-map imaging at threshold, and laser scanning photodetachment experiments. This uncovers a wide variety of different vibrational and rotational autodetaching resonances. By examination of both sides of the problem, absorption from the anion to the dipole-bound state and vibrational/rotational autodetachment to the neutral, a complete model of the dipole-bound chemistry is formed. Precise values for the electron affinity EA = 12468.9(1) cm-1, dipole binding energy DBE = 40.2(3) cm-1, and anion inversion splitting ω5 = 115.9(2) cm-1 are obtained. This model is then employed to study possible astronomical implications, revealing good agreement between the K = 1 â 0 CH2CN- dipole transition and the λ8040 diffuse interstellar band.
RESUMEN
The Abel transform is a mathematical operation that transforms a cylindrically symmetric three-dimensional (3D) object into its two-dimensional (2D) projection. The inverse Abel transform reconstructs the 3D object from the 2D projection. Abel transforms have wide application across numerous fields of science, especially chemical physics, astronomy, and the study of laser-plasma plumes. Consequently, many numerical methods for the Abel transform have been developed, which makes it challenging to select the ideal method for a specific application. In this work, eight published transform methods have been incorporated into a single, open-source Python software package (PyAbel) to provide a direct comparison of the capabilities, advantages, and relative computational efficiency of each transform method. Most of the tested methods provide similar, high-quality results. However, the computational efficiency varies across several orders of magnitude. By optimizing the algorithms, we find that some transform methods are sufficiently fast to transform 1-megapixel images at more than 100 frames per second on a desktop personal computer. In addition, we demonstrate the transform of gigapixel images.
RESUMEN
Vinylidene-acetylene isomerization is the prototypical example of a 1,2-hydrogen shift, one of the most important classes of isomerization reactions in organic chemistry. This reaction was investigated with quantum state specificity by high-resolution photoelectron spectroscopy of the vinylidene anions H2CC- and D2CC- and quantum dynamics calculations. Peaks in the photoelectron spectra are considerably narrower than in previous work and reveal subtleties in the isomerization dynamics of neutral vinylidene, as well as vibronic coupling with an excited state of vinylidene. Comparison with theory permits assignment of most spectral features to eigenstates dominated by vinylidene character. However, excitation of the ν6 in-plane rocking mode in H2CC results in appreciable tunneling-facilitated mixing with highly vibrationally excited states of acetylene, leading to broadening and/or spectral fine structure that is largely suppressed for analogous vibrational levels of D2CC.
RESUMEN
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 image.
RESUMEN
We present a comprehensive photoelectron imaging study of the O(2)(X (3)Σ(g)(-),v(')=0-6)âO(2)(-)(X (2)Π(g),v(")=0) and O(2)(a (1)Δ(g),v(')=0-4)âO(2)(-)(X (2)Π(g),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. A 82, 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. A 23, 2866 (1981)]. For both bands, the photoelectron anisotropy parameter variation with electron kinetic energy, ß(E), displays the characteristics of photodetachment from a d-like orbital, consistent with the π(g)(∗) 2p highest occupied molecular orbital of O(2)(-). However, differences exist between the ß(E) trends for detachment into different vibrational levels of the X (3)Σ(g)(-) and a (1)Δ(g) electronic states of O(2). 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 O(2): 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.