Configuration Interaction Approach Research Articles

Nuclear-Electronic Orbital Time-Dependent Configuration Interaction Method.

Combining real-time electronic structure with the nuclear-electronic orbital (NEO) method has enabled the simulation of complex nonadiabatic chemical processes. However, accurate descriptions of hydrogen tunneling and double excitations require multiconfigurational treatments. Herein, we develop and implement the real-time NEO time-dependent configuration interaction (NEO-TDCI) approach. Comparison to NEO-full CI calculations of absorption spectra for a molecular system shows that the NEO-TDCI approach can accurately capture the tunneling splitting associated with the electronic ground state as well as vibronic progressions corresponding to double electron-proton excitations associated with excited electronic states. Both of these features are absent from spectra obtained with single reference real-time NEO methods. Our simulations of hydrogen tunneling dynamics illustrate the oscillation of the proton density from one side to the other via a delocalized, bilobal proton wave function. These results indicate that the NEO-TDCI approach is highly suitable for studying hydrogen tunneling and other inherently multiconfigurational systems.

Investigation of Isolated IrF5 -, IrF6 - Anions and M[IrF6] (M=Na, K, Rb, Cs) Ion Pairs by Matrix-Isolation Spectroscopy and Relativistic Quantum-Chemical Calculations.

The molecular IrF5 -, IrF6 - anions and M[IrF6] (M=Na, K, Rb, Cs) ion pairs were prepared by co-deposition of laser-ablated alkali metal fluorides MF with IrF6 and isolated in solid neon or argon matrices under cryogenic conditions. The free anions were obtained as well by co-deposition of IrF6 with laser-ablated metals (Ir or Pt) as electron sources. The products were characterized in a combined analysis of matrix IR spectroscopy and electronic structure calculations using two-component quasi-relativistic DFT methods accounting for spin-orbit coupling (SOC) effects as well as multi-reference configuration-interaction (MRCI) approaches with SOC. Inclusion of SOC is crucial in the prediction of spectra and properties of IrF6 - and its alkali-metal ion pairs. The observed IR bands and the computations show that the IrF6 - anion adopts an Oh structure in a nondegenerate ground state stabilized by SOC effects, and not a distorted D4h structure in a triplet ground state as suggested by scalar-relativistic calculations. The corresponding "closed-shell" M[IrF6] ion pairs with C3v symmetry are stabilized by coordination of an alkali metal ion to three F atoms, and their structural change in the series from M=Na to Cs was proven spectroscopically. There is no evidence for the formation of IrF7, IrF7 - or M[IrF7] (M=Na, K, Rb, Cs) ion pairs in our experiments.

The 3d 2 D 5/2−2 D 3/2 magnetic dipole transition in potassium-like ions

Spectral lines of the magnetic-dipole transition between the 3d2D3/2,5/2 levels of K-like Kr17+, Zr21+, Nb22+, Mo23+, and Ru25+ ions were measured in a compact electron beam ion trap. By means of dedicated calibration methods, the transition wavelengths of Kr17+, Zr21+, and Mo23+ ions reduce uncertainties by at least one order of magnitude and the wavelengths of Nb22+ and Ru25+ ions are measured for the first time at a few ppm level. In addition, the fine-structure energy splittings were systematically calculated using the multiconfiguration Dirac–Hartree–Fock method combined with the relativistic configuration interaction approach. The contributions of the core-valence and core-core electron correlations, the Breit interaction and QED effect were discussed in detail. The results show that it is essential to include deep core-valence correlation of L-shell and core-core valence correlation of 3p subshell to obtain an agreement better than 0.15% with existing experimental values. The calculation model can be performed to predict the wavelength within a high accuracy for a wide range of potassium-like ions.

Excitation and recombination studies with silicon and sulphur ions at an EBIT

Measurements of electron-impact excitation and recombination rate coefficients of highly charged Si and S ions at the Stockholm electron beam ion trap are reported. The experimental method was a combination of photon detection from the trapped ions during probing and subsequently extraction and time-of-flight (TOF) charge analysis of these ions. The TOF technique allows to measure recombination rate coefficients separately for every charge state, and together with the photon spectra of these ions also the excitation rate coefficients. In this paper, we present more details of the experimental procedure and summarize the experimental results in comparison with two different state-of-the-art calculations of recombination and excitation rates for Si10+–Si13+ and S12+–S15+ ions. One of these uses a relativistic configuration interaction approach (flexible atomic code) and the other is a relativistic many-body perturbation theory. A good to excellent agreement with both of them is found in energy and resonance strength for the investigated ions.

Investigation of optical spectroscopy in W13+ ions

This study presents the investigation of magnetic dipole transition lines of W13+ ions in the wavelength range of 200–700 nm at a low-energy electron beam ion trap. Seventeen lines emitted from W13+ ions have been observed with three being reported experimentally for the first time. The atomic structure calculation and spectra simulation of W13+ ions have been carried out using the multiconfiguration Dirac–Hartree–Fock method combined with the relativistic configuration interaction approach and the collisional–radiative model, respectively. The theoretical calculations are in reasonable agreement with the experimental observations, and most of the observed lines have been identified.

Optical, thermal and semiempirical study of Samarium bi-tartrate trihydrate

In this comprehensive study, we investigated the structure, optical, and thermal aspects of [Sm(C4H5O6)(C4H4O6)][3H2O], a samarium based metal-organic framework. Testing and exploring advanced semiempirical quantum models, we provide some insights into ground-state molecular properties within the solid metal-organic framework. The single-excitation configuration interaction approach within the spectroscopic method INDO/S-CIS was utilized in the computation of UV spectra, singlet, and triplet excited states for the uncoordinated organic component. We also exploited the established Judd-Ofelt theory to elucidate the spectroscopic properties, allowing us to predict various attributes, including absorption and luminescence traits. The inclusion of thermogravimetric analysis exposes a multifaceted thermal decomposition process. Moreover, this analysis was explored in the determination of activation energies associated with distinct stages of decomposition.

A nuclear configuration interaction approach to study nuclear spin effects: an application to ortho- and para-3 He2 @C60.

We introduce a non-orthogonal configuration interaction approach to investigate nuclear quantum effects on energies and densities of confined fermionic nuclei. The Hamiltonian employed draws parallels between confined systems and many-electron atoms, where effective non-Coulombic potentials represent the interactions of the trapped particles. One advantage of this method is its generality, as it offers the potential to study the nuclear quantum effects of various confined species affected by effective isotropic or anisotropic potentials. As a first application, we analyze the quantum states of two 3 He atoms encapsulated in C60 . At the Hartree-Fock level, we observe the breaking of spin and spatial symmetries. To ensure wavefunctions with the correct symmetries, we mix the broken-symmetry Hartree-Fock states within the non-orthogonal configuration interaction expansion. Our proposed approach predicts singly and triply degenerate ground states for the singlet (para-3 He2 @C60 ) and triplet (ortho-3 He2 @C60 ) nuclear spin configurations, respectively. The ortho-3 He2 @C60 ground state is 5.69 cm-1 higher in energy than the para-3 He2 @C60 ground state. The nuclear densities obtained for these states exhibit the icosahedral symmetry of the C60 embedding potential. Importantly, our calculated energies for the lowest 85 states are in close agreement with perturbation theory results based on a harmonic oscillator plus rigid rotor model of 3 He2 @C60 .

Resilience-economy-environment equilibrium based configuration interaction approach towards distributed energy system in energy intensive industry parks

Because unexpected, high-impact, extreme events and disasters can seriously threaten power system safety and resilience, there has been an increased research focus on power system resilience. This study proposes a bi-level multi-objective model for industrial park distributed energy configuration optimization to deal with extreme events, which considers the interactions between the authority and the industrial park in a leader–follower decision process and seeks to trade-off between economic cost, environmental protection, and power system resilience. An interactive algorithm is designed and the ɛ-constraint method is used to convert the model into a bi-level single objective model to solve the proposed complex model. A case example from an industrial park in Wuxi, Jiangsu Province, China, is given to demonstrate the practicality and efficiency of the proposed optimization method. The joint analysis of the power supply and financial losses found that a distributed energy system with an optimal resilience configuration could guarantee 95.85% of demand for three consecutive hours after an extreme event, maintain more than 50% of demand at any time, and reduce power outage financial losses at any time to a minimum of 0.232 million CNY. Based on the analyses and discussion, this model was proven to provide a reasonable and practical strategy for a resilience-economy-environment trade-off in industrial park distributed energy systems.

Modular Approach to Selected Configuration Interaction in an Arbitrary Spin Basis: Implementation and Comparison of Approaches.

A modular selected configuration interaction (SCI) code has been developed that is based on the existing Monte-Carlo configuration interaction code (MCCI). The modularity allows various selection protocols to be implemented with ease and allows for fair comparison between wave functions built via different criteria. We have initially implemented adaptations of existing SCI theories, which are based on either energy- or coefficient-driven selection schemes. These codes have been implemented not only in the basis of Slater determinants (SDs) but also in the basis of configuration state functions (CSFs) and extended to state-averaged regimes. This allows one to take advantage of the reduced dimensionality of the wave function in the CSF basis and also the guarantee of pure spin states. All SCI methods were found to be able to predict potential energy surfaces to high accuracy, producing compact wave functions, when compared to full configuration interaction (FCI) for a variety of bond-breaking potential energy surfaces. The compactness of the error-controlled adaptive configuration interaction approach, particularly in the CSF basis, was apparent with nonparallelity errors within chemical accuracy while containing as little as 0.02% of the FCI CSF space. The size-to-accuracy was also extended to FCI spaces approaching one billion configurations.

Shape and quantum size effects on the electronic structure, oscillator strengths and state lifetimes of helium-like quantum dots

Transition energies, electric static polarizability, oscillator strengths and state lifetimes of helium-like quantum dots are determined as a function of their shape and size. A configuration interaction approach based on B-spline functions is used. We found that, the oscillator strengths present an extremum around a low value of the dot radius whatever the shape of the confining potential. This extremum is due to the pressure on the energy levels in such a way that for a particular value of the dot radius, the second electron in the excited one-electron state reaches the borders of the confinement potential. The extremum position depends on the impurity charge and the oscillator strength value at this point changes with the potential well shape. As well, the increase of the effective mass involves the shift of the position of the oscillator strength extremum towards weak radius values. The first excited state lifetime globally increases with the dot radius and the reduction of the nuclear charge but presents a shoulder for a certain low value of the dot radius mostly marked for a triangular form of the confining potential.

A Nonorthogonal Configuration Interaction Approach to Singlet Fission in Perylenediimide Compounds.

Perylenediimide molecules constitute a family of chromophores that undergo singlet fission, a process in which an excited singlet state converts into lower energy triplets on two neighboring molecules, potentially increasing the efficiency of organic solar cells. Here, the nonorthogonal configuration interaction method is applied to study the effect of the different crystal packing of various perylenediimide derivatives on the relative energies of the singlet and triplet states, the intermolecular electronic couplings, and the relative rates for singlet fission. The analysis of the wave functions and electronic couplings reveals that charge transfer states play an important role in the singlet fission mechanism. Dimer conformations where the PDI molecules are at large displacements along the long axis and short on the short axis are posed as the most favorable for singlet fission. The role of the substituent at the imide group has been inspected concluding that, although it has no effect in the energies, for some conformations it significantly influences the electronic couplings, and therefore, replacing this substituent with hydrogen may introduce artifacts in the computational modeling of the PDI molecules.

Theoretical investigation of electron capture processes in slow O7+–H collisions

Aims. The total and n-, l-, and S -resolved single-electron-capture cross sections for the collisions of O7+ with atomic hydrogen are studied in the energy region from 10−3eV u−1−5keV u−1. Methods. These state-selective cross sections were calculated by employing the full quantum-mechanical molecular-orbital close-coupling (QMOCC) method. The ab initio multireference single- and double-excitation configuration interaction approach, with optimized atomic basis sets to accurately describe the highly excited states, was used to obtain the adiabatic potentials and the radial and rotational coupling matrix elements that are required in the QMOCC calculation. Results. Our results are compared with other available theoretical and experimental data. The n = 5 manifold is the dominant reaction channel for the chasrge-transfer process for this collision system over the entire energy range, and our results agree better with the experimental data than the other theoretical results in the energy region in which they overlap because we included the necessary highly excited states in the expansion basis set. These charge-exchange cross-section data are useful for understanding and modeling the X-ray emission in astrophysical environments.

(Invited) On-the-Fly Non-Adiabatic Dynamics Simulations of Single-Walled Carbon Nanotubes with Covalent Defects

Single-walled carbon nanotubes (SWCNTs) with covalent surface defects have been explored recently due to their promise for use in single-photon telecommunication emission and in spintronic applications. The dynamical evolution of excitons (the primary electronic excitations) in these systems has only been loosely explored using atomistic modeling due to the size-limitations of these large systems. We present computational modeling of non-radiative relaxation on a variety of SWCNT chiralities with single-defect functionalization schemes. Our modeling uses a trajectory surface hopping algorithm accounting for excitonic effects with a configuration interaction approach. We find a strong chirality and defect-composition dependence on the population relaxation (50 – 500 fs) between the nanotube band-gap excitation and the defect-associated, single-photon-emitting state, giving insight into the dynamic trapping nature of these localized excitonic states. Engineering fast population decay into the quasi-two-level sub-system with weak coupling to higher-energy states increases the effectiveness and controllability of these quantum light emitters.

Schematic model for induced fission in a configuration-interaction approach

Schematic model for induced fission in a configuration-interaction approach

A relativistic configuration interaction method with general expansions and initial applications to electronic g-factors.

A new implementation of the orbital-based two-component relativistic configuration interaction approach is reported and applied to calculations of the electronic g-shifts of three diatomic radicals: AlO, HgF, and PdH. The new implementation augments efficient routines for the calculation of nonrelativistic Hamiltonians with new vectorized routines for the calculation of the action of the one-electron spin-orbit operator and allows efficient calculations for the expansion of generalized active space type. The program makes full use of double group as well as time-reversal symmetry. Particle-hole reorganization of the operators is used to improve the efficiency for expansions with nearly fully occupied orbital spaces. The flexibility of the algorithm and program is used to investigate the convergence of electronic g-shifts for the three diatomic radicals as functions of the active space, states included in the orbital optimization, and excitation levels. It was possible to converge to the valence limits within a few percent using expansions containing up to quadruple excitations. However, when excitations from the core orbitals were added, it was not possible to demonstrate convergence to within a few percent with expansions containing at most 10 × 109 determinants.

Vibrational Predissociation Spectra of C2 N- and C3 N- : Bending and Stretching Vibrations.

We present infrared predissociation spectra of C2 N- (H2 ) and C 3 N- (H2 ) in the 300-1850 cm-1 range. Measurements were performed using the FELion cryogenic ion trap end user station at the Free Electron Lasers for Infrared eXperiments (FELIX) laboratory. For C2 N- (H2 ), we detected the CCN bending and CC-N stretching vibrations. For the C3 N- (H2 ) system, we detected the CCN bending, the CC-CN stretching, and multiple overtones and/or combination bands. The assignment and interpretation of the presented experimental spectra is validated by calculations of anharmonic spectra within the vibrational configuration interaction (VCI) approach, based on potential energy surfaces calculated at explicitly correlated coupled cluster theory (CCSD(T)-F12/cc-pVTZ-F12). The H2 tag acts as an innocent spectator, not significantly affecting the C2,3 N- bending and stretching mode positions. The recorded infrared predissociation spectra can thus be used as a proxy for the vibrational spectra of the bare anions.

Calculations of multipole transitions in Sn II for kilonova analysis

We use the method that combines linearized coupled-cluster and configuration interaction approaches for calculating energy levels and multipole transition probabilities in singly ionized tin ions. We show that our calculated energies agree very well with the experimental data. We present probabilities of magnetic dipole and electric quadrupole transitions and use them for the analysis of the AT2017gfo kilonova emission spectra. This study demonstrates the importance and utility of accurate atomic data for forbidden transitions in the examination of future kilonova events.Graphical abstract

Approximate computations of linear and nonlinear polarizabilities for conjugated systems within a configuration interaction approach

Approximate computations of linear and nonlinear polarizabilities for conjugated systems within a configuration interaction approach

MP-CITDSE: A set of ab-initio programs for the simulation of hydrogenic and helium-like atom-laser interactions

MP-CITDSE is a package of programs which solves the time-dependent Schrödinger equation for hydrogenic and helium-like atomic systems interacting with an ultra-short laser pulse (of attosecond or femtosecond duration). The output of the computations – with some minimal processing – may be used to calculate excited populations, single and double ionisation yields, kinetic, angular and radial electron distributions, and harmonic yields. For the Helium atom, a full account of the inter-electronic correlation effects is included via a configuration interaction approach; for the time propagation of the wavefunction a spectral basis expansion on the eigenstates of the field-free Hamiltonian is used; for this reason post-processing of the expansion coefficients just after the pulse lead to simple formulas for quantities of experimental interest. Program summaryProgram Title: MP-CITDSECPC Library link to program files:https://doi.org/10.17632/gv4zxmfdx3.1Developer's repository link:https://github.com/aforembs/MP-CITDSELicensing provisions: GPLv3Programming language: C++Nature of problem: The ultra-fast high-intensity laser pulses of modern experimental sources require an ab-initio theoretical treatment, as the characteristics of such pulses are generally incompatible with the established Lowest-order Perturbation Theory (LOPT) approximation. Such a treatment can be quite cumbersome to not only implement, but also describe in a clear, intuitive manner. Its inherent complexity ensures that even in its simplest form, an ab-initio TDSE solver can easily consist of several thousand lines of code. As with any project of such scope a significant amount of effort is required to keep the code up to date, running on several platforms, compilers and operating systems. As such, while the numerical problem tackled by MP-CITDSE is that of the simulation of hydrogenic and helium-like atom-laser interactions on a single node computer/workstation; its main challenges are longevity and expandability. By doing away with unnecessary abstractions within the code, using a modern standard of a widely used and performant language (C++ 17) and hosting the source code on a publicly available GitHub repository we hope that the programs provided herein prove themselves useful to many current and future AMO Physicists.Solution method: The atomic systems are considered confined in a spherical box of finite size. In the one-electron case (hydrogen) the eigenstates are calculated in a spherical coordinate system by the direct diagonalisation of the field-free Hamiltonian matrix representation on a B-splines piecewise polynomial basis expansion of the radial part of the eigenfunctions; for the two-electron case (helium) the numerically calculated one-electron eigenstates are angularly coupled to form a zero-order (uncorrelated) two-electron numerical basis; then the latter basis is further coupled via a configuration-interaction approach to eventually calculate the helium's two-electron eigenstates.Following these steps, for both systems (hydrogen and helium) the computation proceeds by expanding the time-dependent wavefunction on the corresponding field-free eigenstate basis; thus, we end up to a system of first-order ordinary differential equations (ODEs) in time for the expansion (time-dependent) coefficients; the dynamical parameters for the ODEs time propagation, namely the eigenenergies and dipole matrix elements are calculated only once prior to the ODEs propagation [2]. The structure of the propagating matrix is block tridiagonal.Additional comments including restrictions and unusual features: This paper serves as the definitive reference for the MP-CITDSE code. In this version we solve the ODEs using a Runge-Kutta-Felnberg (RKF) algorithm. Also we have restricted the code to treat hydrogen and helium but with very little effort (non-relativistic) hydrogenic and helium-like atomic systems can also be simulated. The programs are supplied with two methods of compilation, via make and cmake to ensure greater portability.

A parallel, distributed memory implementation of the adaptive sampling configuration interaction method.

The many-body simulation of quantum systems is an active field of research that involves several different methods targeting various computing platforms. Many methods commonly employed, particularly coupled cluster methods, have been adapted to leverage the latest advances in modern high-performance computing. Selected configuration interaction (sCI) methods have seen extensive usage and development in recent years. However, the development of sCI methods targeting massively parallel resources has been explored only in a few research works. Here, we present a parallel, distributed memory implementation of the adaptive sampling configuration interaction approach (ASCI) for sCI. In particular, we will address the key concerns pertaining to the parallelization of the determinant search and selection, Hamiltonian formation, and the variational eigenvalue calculation for the ASCI method. Load balancing in the search step is achieved through the application of memory-efficient determinant constraints originally developed for the ASCI-PT2 method. The presented benchmarks demonstrate near optimal speedup for ASCI calculations of Cr2 (24e, 30o) with 106, 107, and 3 × 108 variational determinants on up to 16 384 CPUs. To the best of the authors' knowledge, this is the largest variational ASCI calculation to date.