Calculations for doubly-excited states populated in two-electron processes

Recent calculations of doubly-excited states for two and four-electron states in neutral atoms and ions are described. In particular the radiative properties of these states are considered. It is pointed out that some of these states live so long that triply-excited states perhaps can be formed in neutralisation processes at surfaces. © 1991 Springer-Verlag.

yambo: An ab initio tool for excited state calculations

yambo is an ab initio code for calculating quasiparticle energies and optical properties of electronic systems within the framework of many-body perturbation theory and time-dependent density functional theory. Quasiparticle energies are calculated within the GW approximation for the self-energy. Optical properties are evaluated either by solving the Bethe-Salpeter equation or by using the adiabatic local density approximation. yambo is a plane-wave code that, although particularly suited for calculations of periodic bulk systems, has been applied to a large variety of physical systems. yambo relies on efficient numerical techniques devised to treat systems with reduced dimensionality, or with a large number of degrees of freedom. The code has a user-friendly command-line based interface, flexible 110 procedures and is interfaced to several publicly available density functional ground-state codes.

The transport of cosmic rays in self-excited magnetic turbulence

The process of diffusive shock acceleration relies on the efficacy with which hydromagnetic waves can scatter charged particles in the precursor of a shock. The growth of self-generated waves is driven by both resonant and non-resonant processes. We perform high-resolution magnetohydrodynamic simulations of the non-resonant cosmic ray driven instability, in which the unstable waves are excited beyond the linear regime. In a snapshot of the resultant field, particle transport simulations are carried out. The use of a static snapshot of the field is reasonable given that the Larmor period for particles is typically very short relative to the instability growth time. The diffusion rate is found to be close to, or below, the Bohm limit for a range of energies. This provides the first explicit demonstration that self-excited turbulence reduces the diffusion coefficient and has important implications for cosmic-ray transport and acceleration in supernova remnants.

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. I. General formalism and application to open-shell states

The solution of the time-dependent Schrodinger equation for systems of interacting electrons is generally a prohibitive task, for which approximate methods are necessary. Popular approaches, such as the time-dependent Hartree-Fock (TDHF) approximation and time-dependent density functional theory (TDDFT), are essentially single-configurational schemes. TDHF is by construction incapable of fully accounting for the excited character of the electronic states involved in many physical processes of interest; TDDFT, although exact in principle, is limited by the currently available exchange-correlation functionals. On the other hand, multiconfigurational methods, such as the multiconfigurational time-dependent Hartree-Fock (MCTDHF) approach, provide an accurate description of the excited states and can be systematically improved. However, the computational cost becomes prohibitive as the number of degrees of freedom increases, and thus, at present, the MCTDHF method is only practical for few-electron systems. In this work, we propose an alternative approach which effectively establishes a compromise between efficiency and accuracy, by retaining the smallest possible number of configurations that catches the essential features of the electronic wavefunction. Based on a time-dependent variational principle, we derive the MCTDHF working equation for a multiconfigurational expansion with fixed coefficients and specialise to the case of general open-shell states, which are relevant for many physical processes of interest. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3600397]

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. II. Coulomb interaction effects in single conjugated polymer chains

Conjugated polymers have attracted considerable attention in the last few decades due to their potential for optoelectronic applications. A key step that needs optimisation is charge carrier separation following photoexcitation. To understand better the dynamics of the exciton prior to charge separation, we have performed simulations of the formation and dynamics of localised excitations in single conjugated polymer strands. We use a nonadiabatic molecular dynamics method which allows for the coupled evolution of the nuclear degrees of freedom and of multiconfigurational electronic wavefunctions. We show the relaxation of electron-hole pairs to form excitons and oppositely charged polaron pairs and discuss the modifications to the relaxation process predicted by the inclusion of the Coulomb interaction between the carriers. The issue of charge photogeneration in conjugated polymers in dilute solution is also addressed. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3600404]

The effect of ionization on the populations of excited levels of C IV and C V in tokamak edge plasmas

The main populating and depopulating mechanisms of the excited energy levels of ions in plasmas with densities <10²³-10²⁴ m^-3 are electron collisional excitation from the ion's ground state and radiative decay, respectively, with the majority of the electron population being in the ground state of the ionization stage. Electron collisional ionization is predominately expected to take place from one ground state to that of the next higher ionization stage. However, the question arises as to whether, in some cases, ionization can also affect the excited level populations. This would apply particularly to those cases involving transient events such as impurity influxes in a laboratory plasma. An analysis of the importance of ionization in populating the excited levels of ions in plasmas typical of those found in the edge of tokamaks is undertaken for the C IV and C V ionization stages. The emphasis is on those energy levels giving rise to transitions of most use for diagnostic purposes (n ≤ 5). Carbon is chosen since it is an important contaminant of JET plasmas; it was the dominant low Z impurity before the installation of the ITER-like wall and is still present in the plasma after its installation. Direct electron collisional ionization both from and to excited levels is considered. Distorted-wave flexible atomic code calculations are performed to generate the required ionization cross sections, due to a lack of atomic data in the literature. Employing these data, ionization from excited level populations is not found to be significant in comparison with radiative decay. However, for some energy levels, ionization terminating in the excited level has an effect in the steady-state of the order of the measurement errors (±10%). During transient events, ionization to excited levels will be of more importance and must be taken into account in the calculation of excited level populations. More accurate atomic data, including possible resonance contributions to the cross sections, would tend to increase further the importance of these effects. 

Rydberg structure associated with core-excited autoionizing states of the LiH radical

We have investigated inner-shell excitation of the LiH + molecular ion by electron impact within several different collision models to delineate Rydberg autoionizing resonance structure associated with the LiH + (1σ2σ 2 2 Σ + ) core-excited threshold. The minimal representation requires only the retention of the 1σ and 2σ molecular orbitals, in which the core-excited state involves the promotion of a single electron into the 2σ orbital. This model is extended to include two further representations, in which both the 3σ and 4σ orbitals obtained from a self-consistent field calculation improve target representation, correlation and support additional autoionization channels. This affects the autoionization widths and to a lesser degree the positions of the LiH (1σ2σ 2 n s, n p 1,3 Σ + ) resonance series. Comparing our work with calculations on the counterpart atomic Be system assists in the assignment of the core-excited molecular resonance states. The results from our investigation provide helpful insights into the study of inner-shell transitions produced by electron or photon impact in more complex diatomic molecules.

Non-equilibrium modeling of the FE XVII 3C/3D Line Ratio in an Intense X-ray Free-electron Laser Excited Plasma

Recent measurements using an X-ray Free Electron Laser (XFEL) and an Electron Beam Ion Trap at the Linac Coherent Light Source facility highlighted large discrepancies between the observed and theoretical values for the Fe XVII 3C/3D line intensity ratio. This result raised the question of whether the theoretical oscillator strengths may be significantly in error, due to insufficiencies in the atomic structure calculations. We present time-dependent spectral modeling of this experiment and show that non-equilibrium effects can dramatically reduce the predicted 3C/3D line intensity ratio, compared with that obtained by simply taking the ratio of oscillator strengths. Once these non-equilibrium effects are accounted for, the measured line intensity ratio can be used to determine a revised value for the 3C/3D oscillator strength ratio, giving a range from 3.0 to 3.5. We also provide a framework to narrow this range further, if more precise information about the pulse parameters can be determined. We discuss the implications of the new results for the use of Fe XVII spectral features as astrophysical diagnostics and investigate the importance of time-dependent effects in interpreting XFEL-excited plasmas.

Electron-impact ionization of the metastable excited states of Li +

Electron-impact ionization cross sections for the 1s2s 1S and 1s2s 3S metastable states of Li+ are calculated using both perturbative distorted-wave and non-perturbative close-coupling methods. Term-resolved distorted-wave calculations are found to be approximately 15% above term-resolved R-matrix with pseudostates calculations. On the other hand, configuration-average time-dependent close-coupling calculations are found to be in excellent agreement with the configuration-average R-matrix with pseudostates calculations. The non-perturbative R-matrix and close-coupling calculations provide a benchmark for experimental studies of electron-impact ionization of metastable states along the He isoelectronic sequence.

The validity of classical trajectory and perturbative quantal methods for electron-impact ionization from excited states in H-like ions

To test the validity of classical trajectory and perturbative quantal methods for electron-impact ionization of H-like ions from excited states, we have performed advanced close-coupling calculations of ionization from excited states in H, Li 2+ and B 4+ using the R -matrix with pseudo states and the time-dependent close-coupling methods. Comparisons with our classical trajectory Monte Carlo (CTMC) and distorted-wave (DW) calculations show that the CTMC method is more accurate than the DW method for H, but does not improve with n and grows substantially worse with Z , while the DW method improves with Z and grows worse with n .