Elastic and inelastic low-energy electron scattering from pyridine.

A comprehensive investigation of elastic and inelastic electron scattering from molecular pyridine is reported using the ab initio R-matrix method with the static exchange plus polarization and close-coupling approximations for incident energies up to 10 eV. The two well-known low-lying 1 2B1 and 1 2A2 shape resonances as well as a 2 2B1 mixed-character resonance compare well with the theoretical and experimental results. We also detect five core-excited resonances (1 2A1, 1 2B2, 3 2B1, 2 2A2, and 4 2B1), which lie above the first electronic excitation threshold. The total elastic cross sections and momentum transfer cross sections agree reasonably with previous reference data. Comparisons of the differential elastic cross sections of pyridine with those measured for benzene, pyrazine, and pyrimidine show remarkable agreement at scattering angles above 40° but behave differently for forward scattering below 40° below 6 eV, due to the dominant effect of the permanent dipole moment on the differential cross section in the low energy region with narrow scattering angles. Inelastic electronic excitation cross sections are presented, showing the influence of core-excited resonances below the ionization threshold for the first time.

Ionisation of PF3: absolute partial electron ionisation cross sections and the formation and reactivity of dication states.

Absolute partial electron ionisation cross sections, and precursor-specific partial electron ionisation cross sections, for the formation of cations from phosphorus trifluoride (PF3) are reported over the electron energy range 50-200 eV. The absolute values are determined by the measurement of cross sections relative to the formation of PF3+ using 2D ion-ion coincidence time-of-flight mass spectrometry and subsequent scaling using binary encounter-Bethe calculations of the total ionisation cross section. This new dataset significantly augments the partial ionisation cross sections for electron ionization of PF3 found in literature, addressing previous discrepancies in the branching ratios of product ions, and provides the first values for the precursor-specific cross sections. Comparisons to calculated cross sections from the literature are encouraging, although there are discrepancies for individual ions. The coincidence experiments indicate that double and triple ionisation generate approximately 20% of the cationic ionisation products at 200 eV electron energy. One dissociative dication state, dissociating to PF2+ + F+, is clearly identified as the lowest triplet state of PF32+ and five different dications (PF32+, PF22+, PF2+, P2+ and F2+) are detected in the mass spectra. The dication energetics revealed by the experiments are supported by a computational investigation of the dication's electronic structure. The cross sections reported will allow more accurate modelling of the role of the ionization of PF3 in energetic environments. A first investigation of the bimolecular reactivity of metastable states of PF32+ is also reported. In collisions with Ar, O2 and CO dissociative single electron transfer dominates the product ion yield, whereas collision-induced dissociation of the dication is important following collisions with Ne. Consideration of the energetics of these processes indicates that the reactant dication beam contains ions in both the ground singlet state and the first excited triplet state. The deduction regarding the longevity of the triplet state is supported by metastable signals in the coincidence spectra. Weak signals corresponding to the formation of ArF+ are detected following PF32+ collisions with Ar, and experimental and computational considerations indicate this new chemical bond is formed via a collision complex.

The efficient calculation of electron impact ionization cross sections with effective core potentials.

A black box Binary Encounter Bethe (BEB) with an effective core potential (ECP) procedure is implemented, which facilitates the efficient calculation of electron impact ionization cross sections for molecules that include heavy atoms. This is available in the Quantemol electron collisions software, a user friendly graphical user interface to the UKRMol+ codes. Tests were performed for the following series of molecules: CF4, CCl4, CBr4, CI4, and CAt4; CH4, SiH4, GeH4, and SnH4; PH3, PF3, and PCl3; SiCl4 and BCl3; and CH3Br and CF3I. Use of an ECP generally raises the predicted ionization cross section at lower energies leading to improved agreement with experiment compared to all electron calculations for BEB cross sections. Scaling BEB cross sections by the polarizability of the target molecule is shown to give somewhat erratic results, which do not always provide closer agreement with the measured cross sections.

Time-resolved pump-probe spectroscopy with spectral domain ghost imaging.

An atomic-level picture of molecular and bulk processes, such as chemical bonding and charge transfer, necessitates an understanding of the dynamical evolution of these systems. On the ultrafast timescales associated with nuclear and electronic motion, the temporal behaviour of a system is often interrogated in a 'pump-probe' scheme. Here, an initial 'pump' pulse triggers dynamics through photoexcitation, and after a carefully controlled delay a 'probe' pulse initiates projection of the instantaneous state of the evolving system onto an informative measurable quantity, such as electron binding energy. In this paper, we apply spectral ghost imaging to a pump-probe time-resolved experiment at an X-ray free-electron laser (XFEL) facility, where the observable is spectral absorption in the X-ray regime. By exploiting the correlation present in the shot-to-shot fluctuations in the incoming X-ray pulses and measured electron kinetic energies, we show that spectral ghost imaging can be applied to time-resolved pump-probe measurements. In the experiment presented, interpretation of the measurement is simplified because spectral ghost imaging separates the overlapping contributions to the photoelectron spectrum from the pump and probe pulse.

A spectroscopic model for the low-lying electronic states of NO.

The rovibronic structure of A2Σ+, B2Π, and C2Π states of nitric oxide (NO) is studied with the aim of producing comprehensive line lists for its near ultraviolet spectrum. Empirical energy levels for the three electronic states are determined using a combination of the empirical measured active rotation-vibration energy level (MARVEL) procedure and ab initio calculations, and the available experimental data are critically evaluated. Ab initio methods that deal simultaneously with the Rydberg-like A2Σ+ and C2Π and the valence B2Π state are tested. Methods of modeling the sharp avoided crossing between the B2Π and C2Π states are tested. A rovibronic Hamiltonian matrix is constructed using the variational nuclear motion program Duo whose eigenvalues are fitted to the MARVEL. The matrix also includes coupling terms obtained from the refinement of the ab initio potential energy and spin-orbit coupling curves. Calculated and observed energy levels agree well with each other, validating the applicability of our method and providing a useful model for this open shell system.

Quantum Chemistry in Dataflow: Density-Fitting MP2.

We demonstrate the use of dataflow technology in the computation of the correlation energy in molecules at the Møller-Plesset perturbation theory (MP2) level. Specifically, we benchmark density fitting (DF)-MP2 for as many as 168 atoms (in valinomycin) and show that speed-ups between 3 and 3.8 times can be achieved when compared to the MOLPRO package run on a single CPU. Acceleration is achieved by offloading the matrix multiplications steps in DF-MP2 to Dataflow Engines (DFEs). We project that the acceleration factor could be as much as 24 with the next generation of DFEs.

Analysis of a measurement scheme for ultrafast hole dynamics by few femtosecond resolution X-ray pump-probe Auger spectroscopy.

Ultrafast hole dynamics created in molecular systems as a result of sudden ionisation is the focus of much attention in the field of attosecond science. Using the molecule glycine we show through ab initio simulations that the dynamics of a hole, arising from ionisation in the inner valence region, evolves with a timescale appropriate to be measured using X-ray pulses from the current generation of SASE free electron lasers. The examined pump-probe scheme uses X-rays with photon energy below the K edge of carbon (275-280 eV) that will ionise from the inner valence region. A second probe X-ray at the same energy can excite an electron from the core to fill the vacancy in the inner-valence region. The dynamics of the inner valence hole can be tracked by measuring the Auger electrons produced by the subsequent refilling of the core hole as a function of pump-probe delay. We consider the feasibility of the experiment and include numerical simulation to support this analysis. We discuss the potential for all X-ray pump-X-ray probe Auger spectroscopy measurements for tracking hole migration.

Rates of exponential decay in systems of discrete energy levels by Stieltjes imaging.

An isolated bound state coupled to a continuum shows an exponential decay of its survival probability. Rates of the exponential decay occurring due to the bound-continuum coupling can be recovered from discretized continuum (L(2)) calculations using a computational technique known as Stieltjes-Chebyshev moment theory or Stieltjes imaging. At the same time, some genuinely discrete level systems, e.g., Bixon-Jortner model, also show an exponential (or approximately exponential) decay of the initially populated level before the onset of quantum revivals. Here, we demonstrate numerically that Stieltjes imaging can be used for calculation of the rates of the exponential decay in such discrete level systems. We apply the Stieltjes imaging technique to the approximately exponential decay of inner-valence vacancies in trans-butadiene in order to show that the breakdown of the molecular orbital picture of ionization in the inner valence region can be physically interpreted as an energy-forbidden Coster-Kronig transition.

High-order harmonic generation spectroscopy of correlation-driven electron hole dynamics.

We show how high-order harmonic generation spectroscopy can be used to follow correlation-driven electron hole dynamics with attosecond time resolution. The technique is applicable both to normal Auger transitions and to electron hole migration processes that do not lead to secondary electron emission. We theoretically simulate the proposed spectroscopy for M(4,5)NN Auger decay in Kr and for correlation-driven inner-valence hole dynamics in trans-butadiene and propanal.

Single-photon laser-enabled auger spectroscopy for measuring attosecond electron-hole dynamics.

We propose and simulate a new type of attosecond time-resolved spectroscopy of electron-hole dynamics, applicable particularly to ultrafast hole migration. Attosecond ionization in the inner-valence region is followed by a vacuum ultraviolet probe inducing single-photon laser-enabled Auger decay, a one-photon-two-electron transition filling the inner-valence vacancy. The double ionization probability as a function of the attosecond pump-vacuum ultraviolet probe delay captures efficiently the ultrafast inner-valence hole dynamics. Detailed ab initio calculations are presented for inner-valence hole migration in glycine.

Benchmark studies of variational, unitary and extended coupled cluster methods.

Comparative benchmark calculations are presented for coupled cluster theory in its standard formulation, as well as variational, extended, and unitary coupled cluster methods. The systems studied include HF, N(2), and CN, and with cluster operators that for the first time include up to quadruple excitations. In cases where static correlation effects are weak, the differences between the predictions of molecular properties from each theory are negligible. When, however, static correlation is strong, it is demonstrated that variational coupled cluster theory can be significantly more robust than the traditional ansatz and offers a starting point on which to base single-determinant reference methods that can be used beyond the normal domain of applicability. These conclusions hold at all levels of truncation of the cluster operator, with the variational approach showing significantly smaller errors.

A linked electron pair functional.

A modification of the variational configuration interaction functional in the first-order interacting space for molecular electronic structure is presented. The modified functional is a fully linked expression that by construction is extensive and invariant to transformations of the underlying orbital basis and is exact for an ensemble of separated two-electron subsystems. In addition, an approximation to variational coupled cluster is generated through truncation of the exponential cluster operator. When combined, these methods demonstrate accuracy that exceeds that of the standard coupled-cluster method, in particular in situations where the reference Slater determinant is not a good approximation.

The Methodist Hospital CCU: a Beacon unit of excellence.

This article features the Coronary Care Unit of The Methodist Hospital of Houston, Texas. This unit was one of the first Beacon Critical Care Units recognized by the American Association of Critical Care Nurses. This article focuses on how to achieve this award. The Coronary Care Unit nursing infrastructure is described, and specific unit examples are included.