Scrutinizing GW-Based Methods Using the Hubbard Dimer.

Using the simple (symmetric) Hubbard dimer, we analyze some important features of the GW approximation. We show that the problem of the existence of multiple quasiparticle solutions in the (perturbative) one-shot GW method and its partially self-consistent version is solved by full self-consistency. We also analyze the neutral excitation spectrum using the Bethe-Salpeter equation (BSE) formalism within the standard GW approximation and find, in particular, that 1) some neutral excitation energies become complex when the electron-electron interaction U increases, which can be traced back to the approximate nature of the GW quasiparticle energies; 2) the BSE formalism yields accurate correlation energies over a wide range of U when the trace (or plasmon) formula is employed; 3) the trace formula is sensitive to the occurrence of complex excitation energies (especially singlet), while the expression obtained from the adiabatic-connection fluctuation-dissipation theorem (ACFDT) is more stable (yet less accurate); 4) the trace formula has the correct behavior for weak (i.e., small U) interaction, unlike the ACFDT expression.

Photoemission Spectra from the Extended Koopman's Theorem, Revisited.

The Extended Koopman's Theorem (EKT) provides a straightforward way to compute charged excitations from any level of theory. In this work we make the link with the many-body effective energy theory (MEET) that we derived to calculate the spectral function, which is directly related to photoemission spectra. In particular, we show that at its lowest level of approximation the MEET removal and addition energies correspond to the so-called diagonal approximation of the EKT. Thanks to this link, the EKT and the MEET can benefit from mutual insight. In particular, one can readily extend the EKT to calculate the full spectral function, and choose a more optimal basis set for the MEET by solving the EKT secular equation. We illustrate these findings with the examples of the Hubbard dimer and bulk silicon.

Optical spectra of 2D monolayers from time-dependent density functional theory.

The optical spectra of two-dimensional (2D) periodic systems provide a challenge for time-dependent density-functional theory (TDDFT) because of the large excitonic effects in these materials. In this work we explore how accurately these spectra can be described within a pure Kohn-Sham time-dependent density-functional framework, i.e., a framework in which no theory beyond Kohn-Sham density-functional theory, such as GW, is required to correct the Kohn-Sham gap. To achieve this goal we adapted a recent approach we developed for the optical spectra of 3D systems [S. Cavo, J. A. Berger and P. Romaniello, Phys. Rev. B, 2020, 101, 115109] to those of 2D systems. Our approach relies on the link between the exchange-correlation kernel of TDDFT and the derivative discontinuity of ground-state density-functional theory, which guarantees a correct quasi-particle gap, and on a generalization of the polarization functional [J. A. Berger, Phys. Rev. Lett., 2015, 115, 137402], which describes the excitonic effects. We applied our approach to two prototypical 2D monolayers, h-BN and MoS2. We find that our protocol gives a qualitatively good description of the optical spectrum of h-BN, whereas improvements are needed for MoS2 to describe the intensity of the excitonic peaks.

Many-Body Effective Energy Theory: Photoemission at Strong Correlation.

In this work, we explore the performance of a recently derived many-body effective energy theory for the calculation of photoemission spectra in the regime of strong electron correlation. We apply the theory to paramagnetic MnO, FeO, CoO, and NiO, which are typical examples of strongly correlated materials and, therefore, a challenge for standard theories. We show that our method opens a correlation gap in all of the oxides studied without breaking the symmetry. Although the materials seem similar, we show that an analysis of the occupation numbers reveals that the nature of the gap is not the same for these materials. Overall, the results are very promising, although improvements are clearly required, since the band gap is overestimated for all of the systems studied. We indicate some possible strategies to further develop the theory.

Reduced density-matrix functional theory: Correlation and spectroscopy.

In this work, we explore the performance of approximations to electron correlation in reduced density-matrix functional theory (RDMFT) and of approximations to the observables calculated within this theory. Our analysis focuses on the calculation of total energies, occupation numbers, removal/addition energies, and spectral functions. We use the exactly solvable Hubbard dimer at 1/4 and 1/2 fillings as test systems. This allows us to analyze the underlying physics and to elucidate the origin of the observed trends. For comparison, we also report the results of the GW approximation, where the self-energy functional is approximated, but no further hypothesis is made concerning the approximations of the observables. In particular, we focus on the atomic limit, where the two sites of the dimer are pulled apart and electrons localize on either site with equal probability, unless a small perturbation is present: this is the regime of strong electron correlation. In this limit, using the Hubbard dimer at 1/2 filling with or without a spin-symmetry-broken ground state allows us to explore how degeneracies and spin-symmetry breaking are treated in RDMFT. We find that, within the used approximations, neither in RDMFT nor in GW, the signature of strong correlation is present, when looking at the removal/addition energies and spectral function from the spin-singlet ground state, whereas both give the exact result for the spin-symmetry broken case. Moreover, we show how the spectroscopic properties change from one spin structure to the other.

Built-in reduction of statistical fluctuations of partitioning objects.

Our theoretical and numerical investigation of the movement of an object that partitions a microtubule filled with small particles indicates that vibrations warranted by thermal equilibrium are reached only after a time that increases exponentially with the number of particles involved. This points to a basic mechanical process capable of breaching, on accessible time scales, the ultimate ergodic constraints that force randomness on bound microscale and nanoscale systems.