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Vacancies in the L1 shell of atoms and molecules can decay non-radiatively via Coster–Kronig decay whereby the vacancy is filled by an electron from the L2,3 shell while a second electron is emitted into the ionization continuum. This process is akin to Auger decay, but in contrast to Auger electrons, Coster–Kronig electrons have rather low kinetic energies of less than 50 eV. In the present work, we extend recently introduced methods for the construction of molecular Auger spectra that are based on complex-scaled equation-of-motion coupled-cluster theory to Coster–Kronig decay. We compute ionization energies as well as total and partial decay widths for the 2s-1 states of argon and hydrogen sulfide and construct the L1L2,3M Coster–Kronig and L1MM Auger spectra of these species. Whereas our final spectra are in good agreement with the available experimental and theoretical data, substantial disagreements are found for various branching ratios suggesting that spin–orbit coupling makes a major impact on Coster–Kronig decay already in the third period of the periodic table. [ABSTRACT FROM AUTHOR]

We investigate the reliability of two cost-effective coupled-cluster methods for computing spin-state energetics and spin-related properties of a set of open-shell transition-metal complexes. Specifically, we employ the second-order approximate coupled-cluster singles and doubles (CC2) method and projection-based embedding that combines equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) with density functional theory (DFT). The performance of CC2 and EOM-CCSD-in-DFT is assessed against EOM-CCSD. The chosen test set includes two hexaaqua transition-metal complexes containing Fe(II) and Fe(III), and a large Co(II)-based single-molecule magnet with a non-aufbau ground state. We find that CC2 describes the excited states more accurately, reproducing EOM-CCSD excitation energies within 0.05 eV. However, EOM-CCSD-in-DFT excels in describing transition orbital angular momenta and spin–orbit couplings. Moreover, for the Co(II) molecular magnet, using EOM-CCSD-in-DFT eigenstates and spin–orbit couplings, we compute spin-reversal energy barriers, as well as temperature-dependent and field-dependent magnetizations and magnetic susceptibilities that closely match experimental values within spectroscopic accuracy. These results underscore the efficiency of CC2 in computing state energies of multi-configurational, open-shell systems and highlight the utility of the more cost-efficient EOM-CCSD-in-DFT for computing spin–orbit couplings and magnetic properties of complex and large molecular magnets. [ABSTRACT FROM AUTHOR]

We compute EOM-EA-CCSD and EOM-EA-CCSDT potential energy curves and one-electron properties of several anions at bond lengths close to where these states become unbound. We compare the anions of HCl and pyrrole, which are associated with s-wave scattering, with N2 and H2, which correspond to resonances. For HCl and pyrrole, we observe, on inclusion of diffuse basis functions, a pronounced bending effect in the anionic potential energy curves near the crossing points with their corresponding neutral molecules. Additionally, we observe that the Dyson orbital and second moment of the electron density become extremely large in this region; for HCl, the size of the latter becomes 5 orders of magnitude larger over a range of 5 pm. This behaviour is not observed in H2 or N2. Our work thus shows that bound state electronic-structure methods can distinguish between anions that turn into electronic resonances and those associated with s-wave scattering states. [ABSTRACT FROM AUTHOR]

Electronic resonances are states that are unstable towards loss of electrons. They play critical roles in high-energy environments across chemistry, physics, and biology but are also relevant to processes under ambient conditions that involve unbound electrons. This feature article focuses on complex-variable techniques such as complex scaling and complex absorbing potentials that afford a treatment of electronic resonances in terms of discrete square-integrable eigenstates of non-Hermitian Hamiltonians with complex energy. Fundamental aspects of these techniques as well as their integration into molecular electronic-structure theory are discussed and an overview of some recent developments is given: analytic gradient theory for electronic resonances, the application of rank-reduction techniques and quantum embedding to them, as well as approaches for evaluating partial decay widths. [ABSTRACT FROM AUTHOR]

Optical cycling, a continuous photon scattering off atoms or molecules, plays a central role in the quantum information science. While optical cycling has been experimentally achieved for many neutral species, few molecular ions have been investigated. We present a systematic theoretical search for diatomic molecular ions suitable for optical cycling using equation-of-motion coupled-cluster methods. Inspired by the electronic structure patterns of laser-cooled neutral molecules, we establish the design principles for molecular ions and explore various possible cationic molecular frameworks. The results show that finding a perfect molecular ion for optical cycling is challenging, yet possible. Among various possible diatomic molecules we suggest several candidates, which require further attention from both theory and experiment: YF+, SiO+, PN+, SiBr+, and BO+. [ABSTRACT FROM AUTHOR]

Anionic states of benzonitrile are investigated by high-level electronic structure methods. The calculations using equation-of-motion coupled-cluster theory for electron-attached states confirm earlier conclusions drawn from the photodetachment experiments wherein the ground state of the anion is the valence 2B1 state, while the dipole bound state lies adiabatically ∼0.1 eV above. Inclusion of triple excitations and zero-point vibrational energies is important for recovering relative state correct ordering. The computed Franck–Condon factors and photodetachment cross-sections further confirm that the observed photodetachment spectrum originates from the valence anion. The valence anion is electronically bound at its equilibrium geometry, but it is metastable at the equilibrium geometry of the neutral. The dipole-bound state, which is the only bound anionic state at the neutral equilibrium geometry, may serve as a gateway state for capturing the electron. Thus, the emerging mechanistic picture entails electron capture via a dipole bound state, followed by non-adiabatic relaxation forming valence anions. [ABSTRACT FROM AUTHOR]

Photoelectron angular distributions determined in small energy increments between 3.522 and 3.650 eV reveal distinctly different detachment mechanisms within the CuF2−(X 1Σ+g) → linear CuF2(X 2Σ+g) + e− band. Certain channels also display non-Franck–Condon behaviour, the action spectra of which reveal rich structure. The behaviour reflects excitation to an electronically unbound anion state (at the linear geometry). The effects of the intermediate state are observed in the detachment behaviour at photon energies down to the X 1Σ+g→ X 2Σ+g threshold. Adiabatic CAP-EOM-CCSD (equation of motion coupled cluster singles and doubles, including a complex absorbing potential) energy curves are presented along the bending coordinate, showing the complexity of anion and neutral states for this system. The photodetachment action spectra represent a spectroscopic probe of the vibronic state energies in the vertical excitation region and highlight the need for treatment of vibronic coupling in systems involving the loss of an electron. [ABSTRACT FROM AUTHOR]

Despite their small size, C2 species pose big challenges to electronic structure methods, owing to extensive electronic degeneracies and multi-configurational wave functions, which lead to a dense manifold of electronic states. We present detailed electronic structure calculations of C2, C2−, and C22−, emphasizing spectroscopically relevant properties. We employ the double ionization potential (DIP) and ionization potential (IP) variants of the equation-of-motion coupled-cluster method with single and double substitutions (EOM-CCSD) and a dianionic reference state. We show that EOM-CCSD is capable of describing multiple interacting states in C2 and C2− in an accurate, robust, and effective way. We also characterize the electronic structure of C22−, which is metastable with respect to electron detachment. [ABSTRACT FROM AUTHOR]