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Aiming at completing the sets of FCI-quality transition energies that we recently developed (

Context. Line shapes of the magnesium resonance lines in white dwarf spectra are determined by the properties of magnesium atoms and the structure of the white dwarf atmosphere. Through their blanketing effect, these lines have a dominant influence on the model structure and thus on the determination from the spectra of other physical parameters that describe the stellar atmosphere and elemental abundances.Aims. In continuation of previous work on Mg+He lines in the UV, we present theoretical profiles of the resonance line of neutral Mg perturbed by He at the extreme density conditions found in the cool largely transparent atmosphere of DZ white dwarfs.Methods. We accurately determined the broadening of Mg by He in a unified theory of collisional line profiles using ab initio calculations of MgHe potential energies and transition matrix elements among the singlet electronic states that are involved for the observable spectral lines.Results. We computed the shapes and line parameters of the Mg lines and studied their dependence on helium densities and temperatures. We present results over the full range of temperatures from 4000 to 12 000 K needed for input to stellar spectra models. Atmosphere models were constructed for a range of effective temperatures and surface gravities typical for cool DZ white dwarfs. We present synthetic spectra tracing the behavior of the Mg resonance line profiles under the low temperatures and high gas pressures prevalent in these atmospheres.Conclusions. The determination of accurate opacity data of magnesium resonance lines together with an improved atmosphere model code lead to a good fit of cool DZ white dwarf stars. The broadening of spectral lines by helium needs to be understood to accurately determine the H/He and Mg/He abundance ratio in DZ white dwarf atmospheres. We emphasize that no free potential parameters or ad hoc adjustments were used to calculate the line profiles.

The Bethe-Salpeter equation (BSE) formalism is a computationally affordable method for the calculation of accurate optical excitation energies in molecular systems. Similar to the ubiquitous adiabatic approximation of time-dependent density-functional theory, the static approximation, which substitutes a dynamical (\ie, frequency-dependent) kernel by its static limit, is usually enforced in most implementations of the BSE formalism. Here, going beyond the static approximation, we compute the dynamical correction of the electron-hole screening for molecular excitation energies thanks to a renormalized first-order perturbative correction to the static BSE excitation energies. The present dynamical correction goes beyond the plasmon-pole approximation as the dynamical screening of the Coulomb interaction is computed exactly within the random-phase approximation. Our calculations are benchmarked against high-level (coupled-cluster) calculations, allowing to assess the clear improvement brought by the dynamical correction for both singlet and triplet optical transitions.

Following the recent work of Eriksen et al. [arXiv:2008.02678], we report the performance of the \textit{Configuration Interaction using a Perturbative Selection made Iteratively} (CIPSI) method on the non-relativistic frozen-core correlation energy of the benzene molecule in the cc-pVDZ basis. Following our usual protocol, we obtain a correlation energy of $-863.4(5)$ m$E_h$ which agrees with the theoretical estimate of $-863$ m$E_h$ proposed by Eriksen et al. using an extensive array of highly-accurate new electronic structure methods.

We calculate interaction constants for the contributions from \PT-odd scalar-pseudoscalar and tensor-pseudotensor operators to the electric dipole moment of ${}^{129}$Xe, for the first time in case of the former, using relativistic many-body theory including the effects of dynamical electron correlations. These interaction constants are necessary ingredients to relating the corresponding measurements to fundamental parameters in models of physics beyond the Standard Model. We obtain $\alpha_{C_S} = \left( 0.71 \pm 0.18 \right) [10^{-23}\, e~\text{cm}]$ and $\alpha_{C_T}= \left( 0.507 \pm 0.048 \right) [10^{-20}\, \left<\Sigma\right>_{\text{Xe}}\, e~\text{cm}]$, respectively. We apply these results to test a phenomenological relation between the two quantities, commonly used in the literature, and discuss their present and future phenomenological impact.

The density matrix renormalization group in chemistry and molecular physics: Recent developments and new challenges The Journal of Chemical Physics 152, 040903 (2020); https://doi. ABSTRACT Taking as an example the simple CH 3 radical, this work demonstrates the cooperative character of the spin-polarization phenomenon of the closed-shell core in free radicals. Spin polarization of CH σ bonds is not additive here, as spin polarization of one bond enhances that of the next bond. This cooperativity is demonstrated by a series of configuration interaction calculations converging to the full valence limit and is rationalized by analytic developments. The same phenomenon is shown to take place in those diradicals where spin polarization plays a major role, as illustrated in square planar carbo-cyclobutadiene C 12 H 4. The treatment of cooperativity represents a challenge for usual post-Hatree-Fock methods. Published under license by AIP Publishing. https://doi.

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Four-component relativistic atomic and molecular calculations are typically performed within the no-pair approximation where negative-energy solutions are discarded. These states are, however, needed in QED calculations, wherein, furthermore, charge conjugation symmetry, which connects electronic and positronic solutions, becomes an issue. In this work, we shall discuss the realization of charge conjugation symmetry of the Dirac equation in a central field within the finite basis approximation. Three schemes for basis set construction are considered: restricted, inverse, and dual kinetic balance. We find that charge conjugation symmetry can be realized within the restricted and inverse kinetic balance prescriptions, but only with a special form of basis functions that does not obey the right boundary conditions of the radial wavefunctions. The dual kinetic balance prescription is, on the other hand, compatible with charge conjugation symmetry without restricting the form of the radial basis functions. However, since charge conjugation relates solutions of opposite value of the quantum number κ, this requires the use of basis sets chosen according to total angular momentum j rather than orbital angular momentum. As a special case, we consider the free-particle Dirac equation, where opposite energy solutions are related by charge conjugation symmetry. We show that there is additional symmetry in that solutions of the same value of κ come in pairs of opposite energy.

By combining density-functional theory (DFT) and wave function theory (WFT) via the range separation (RS) of the interelectronic Coulomb operator, we obtain accurate fixed-node diffusion Monte Carlo (FN-DMC) energies with compact multi-determinant trial wave functions. In particular, we combine here short-range exchange-correlation functionals with a flavor of selected configuration interaction (SCI) known as \emph{configuration interaction using a perturbative selection made iteratively} (CIPSI), a scheme that we label RS-DFT-CIPSI. One of the take-home messages of the present study is that RS-DFT-CIPSI trial wave functions yield lower fixed-node energies with more compact multi-determinant expansions than CIPSI, especially for small basis sets. Indeed, as the CIPSI component of RS-DFT-CIPSI is relieved from describing the short-range part of the correlation hole around the electron-electron coalescence points, the number of determinants in the trial wave function required to reach a given accuracy is significantly reduced as compared to a conventional CIPSI calculation. Importantly, by performing various numerical experiments, we evidence that the RS-DFT scheme essentially plays the role of a simple Jastrow factor by mimicking short-range correlation effects, hence avoiding the burden of performing a stochastic optimization. Considering the 55 atomization energies of the Gaussian-1 benchmark set of molecules, we show that using a fixed value of $\mu=0.5$~bohr$^{-1}$ provides effective error cancellations as well as compact trial wave functions, making the present method a good candidate for the accurate description of large chemical systems.

In this work we show the advantages of using the Coulomb-hole plus screened-exchange (COHSEX) approach in the calculation of potential energy surfaces. In particular, we demonstrate that, unlike perturbative $GW$ and partial self-consistent $GW$ approaches, such as eigenvalue-self-consistent $GW$ and quasi-particle self-consistent $GW$, the COHSEX approach yields smooth potential energy surfaces without irregularities and discontinuities. Moreover, we show that the ground-state potential energy surfaces (PES) obtained from the Bethe-Salpeter equation, within the adiabatic connection fluctuation dissipation theorem, built with quasi-particle energies obtained from perturbative COHSEX on top of Hartree-Fock (BSE@COHSEX@HF) yield very accurate results for diatomic molecules close to their equilibrium distance. When self-consistent COHSEX quasi-particle energies and orbitals are used to build the BSE equation the results become independent of the starting point. We show that self-consistency worsens the total energies but improves the equilibrium distances with respect to BSE@COHSEX@HF. This is mainly due to changes in the screening inside the BSE.

We discuss the physical properties and accuracy of three distinct dynamical (ie, frequency-dependent) kernels for the computation of optical excitations within linear response theory: i) an a priori built kernel inspired by the dressed time-dependent density-functional theory (TDDFT) kernel proposed by Maitra and coworkers, ii) the dynamical kernel stemming from the Bethe-Salpeter equation (BSE) formalism derived originally by Strinati , and iii) the second-order BSE kernel derived by Yang and coworkers . The principal take-home message of the present paper is that dynamical kernels can provide, thanks to their frequency-dependent nature, additional excitations that can be associated to higher-order excitations (such as the infamous double excitations), an unappreciated feature of dynamical quantities. We also analyze, for each kernel, the appearance of spurious excitations originating from the approximate nature of the kernels, as first evidenced by Romaniello. Using a simple two-level model, prototypical examples of valence, charge-transfer, and Rydberg excited states are considered.

The many-body Green's function Bethe-Salpeter equation (BSE) formalism is steadily asserting itself as a new efficient and accurate tool in the ensemble of computational methods available to chemists in order to predict optical excitations in molecular systems. In particular, the combination of the so-called $GW$ approximation of many-body perturbation theory, giving access to reliable ionization energies and electron affinities, and the BSE formalism, able to model UV/Vis spectra by catching excitonic effects, has shown to provide accurate singlet excitation energies in many chemical scenarios with a typical error of $0.1$--$0.3$ eV. With a similar computational cost as time-dependent density-functional theory (TD-DFT), the BSE formalism is able to provide an accuracy on par with the most accurate global and range-separated hybrid functionals without the unsettling choice of the exchange-correlation functional, resolving further known issues (e.g., charge-transfer excitations) and offering a well-defined path to dynamical kernels. In this \textit{Perspective} article, we provide a historical overview of the BSE formalism, with a particular focus on its condensed-matter roots. We also propose a critical review of its strengths and weaknesses in different chemical situations. Future directions of developments and improvements are also discussed.

While Diffusion Monte Carlo (DMC) has the potential to be an exact stochastic method for ab initio electronic structure calculations, in practice the fixed-node approximation and trial wavefunctions with approximate nodes (or zeros) must be used. This approximation introduces a variational error in the energy that potentially can be tested and systematically improved. Here, we present a computational method that produces trial wavefunctions with systematically improvable nodes for DMC calculations of periodic solids. These trial wave-functions are efficiently generated with the configuration interaction using a perturbative selection made iteratively (CIPSI) method, which iteratively selects the most relevant Slater determinants from the full configuration interaction (FCI) space. By introducing a simple protocol combining both exact and approximate finite-supercell results and a controlled extrapolation procedure to reach the thermodynamic limit, we show accurate DMC energies can be obtained using a manageable number of Slater determinants. This approach is illustrated by computing the cohesive energy of carbon diamond in the thermodynamic limit using Slater-Jastrow trial wavefunctions including up to one million Slater determinants.

We present a detailed non-relativistic study of the atoms H, He, C and K and the molecule CH4 in the center of a spherical soft confinement potential of the form VN (r) = (r/r0) N with stiffness parameter N and confinement radius r0. The soft confinement potential approaches the hard-wall limit as N → ∞, giving a more detailed picture of spherical confinement. The confined hydrogen atom is considered as a base model: it is treated numerically to obtain ground-and excited-state energies and nodal positions of the eigenstates to study the convergence towards the hard-wall limit. We also derive some important analytical relations. The use of Gaussian basis sets is analyzed. We find that, for increasing stiffness parameter N , the convergence towards the basis-set limit becomes problematic. As an application, we report dipole polarizabilities for different values of N and r0 of hydrogen. For helium, we determine electron correlation effects with varying N and r0, and discuss the virial theorem for both soft and hard confinements in the limit r0 → 0. For carbon, a change in the orbital population from 2s 2 2p 2 to 2s 0 2p 4 is observed with decreasing r0, while, for potassium, we observe a change from the 2 S to 2 D ground state at small r0 values. For CH4, we show that the one-particle density becomes more spherical with increasing confinement. A possible application of soft confinement to atoms and molecules under high pressure is discussed. Dedicated to Prof. Jürgen Gauss on the occasion of his 60th birthday

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