We develop an improved stochastic formalism for the Bethe-Salpeter equation (BSE), based on an exact separation of the effective-interaction W into two parts, W = (W - vW) + vW, where the latter is formally any translationally invariant interaction, vW(r - r'). When optimizing the fit of the exchange kernel vW to W, using a stochastic sampling W, the difference W - vW becomes quite small. Then, in the main BSE routine, this small difference is stochastically sampled. The number of stochastic samples needed for an accurate spectrum is then largely independent of system size. While the method is formally cubic in scaling, the scaling prefactor is small due to the constant number of stochastic orbitals needed for sampling W.
We present a real-time linear-response approach to solving the dynamical Bethe-Salpeter equation (BSE). The polarization part of the screened interaction is obtained from time-dependent Hartree propagation of the one-particle density matrix within an orbital basis-set representation. The frequency convolution defining the dynamical kernel is evaluated as a product in time, avoiding numerical integration and storage of the full screened Coulomb operator. The resulting nonlinear eigenvalue problem is then solved directly, going beyond the static screening approximation with full-frequency dependence in the screened interaction. We validate the method by calculating the low-lying singlet and triplet excitation energies of water, formaldehyde, and acetylene. While the deterministic scaling remains
O(N6), the time propagation formulation is readily compatible with grid-based stochastic sampling methods, which will open the possibility for dynamical BSE calculations of very large systems.
A formally exact Bethe-Salpeter-like equation for the linear-response function is introduced with a kernel which depends only on the one frequency of the applied field. This is in contrast with the standard Bethe-Salpeter equation (BSE) which involves multiple-frequency integrals over the kernel and response functions. From the one-frequency kernel, known approximations are straightforwardly recovered. However, the present formalism lends itself to more powerful approximations. This is demonstrated with the exact analytical solution of the Hubbard molecule. Similarities and differences of the GW + BSE approach with the self-consistent random-phase approximation are also discussed.
The subject of the thesis focuses on new approximations studied in a formalism based on a perturbation theory allowing to describe the electronic properties of many-body systems in an approximate way. We excite a system with a small disturbance, by sending light on it or by applying a weak electric field to it, for example and the system "responds" to the disturbance, in the framework of linear response, which means that the response of the system is proportional to the disturbance. The goal is to determine what we call the neutral excitations or bound states of the system, and more particularly the single excitations. These correspond to the transitions from the ground state to an excited state. To do this, we describe in a simplified way the interactions of the particles of a many-body system using an effective interaction that we average over the whole system. The objective of such an approach is to be able to study a system without having to use the exact formalism which consists in diagonalizing the N-body Hamiltonian, which is not possible for systems with more than two particles.
Standard many-body perturbation theory for optical excitations combines the
GW approximation for quasiparticle energies with the Bethe-Salpeter equation (BSE) for the electron-hole response. Formally, the BSE kernel must equal the functional derivative of the self-energy,
K=δΣ/δG. In routine practice, however, the kernel is built from a statically screened direct interaction and a bare exchange interaction, which breaks this consistency. Using exact diagonalization of the extended Hubbard dimer, we construct a controlled benchmark that isolates the price of this inconsistency. We show that the internally inconsistent practical
GW+BSE construction frequently yields accurate optical gaps through accidental cancellation between an underestimated
GW gap and an oversized bare-exchange kernel, and we map the regions of parameter space where this accidental accuracy occurs. Upon switching on the nearest-neighbor interaction and binding the exciton, the practical construction remains the accurate one throughout the weak-binding regime, with cancellation optima at parts in
103, while the frozen-
W construction fails at every binding strength. Beyond a binding threshold both static constructions deteriorate, showing that deeply bound excitons require physics beyond any static kernel. Accidental accuracy is therefore a property of the weak-binding regime, and the systematic failure of the frozen-
W derivative kernel within the explored parameter space traces to its overscreening of the exchange channel. The accuracy of the practical kernel is an accidental cancellation of two independent errors, an underestimated quasiparticle gap and an oversized exchange term, not a hidden consistency. These results provide a controlled taxonomy of approximation failure in
GW+BSE and a precise diagnostic for when standard workflows can be trusted.
The correlation energy of an inhomogeneous electron gas is ruled by the density correlation function
L. It obeys a Bethe-Salpeter equation (BSE), whose kernel is the functional derivative of the particle self-energy. It is solved on equal footing for two-particle and single-particle Green's functions within Hedin's GW approximation. According to the Hartree and exchange-correlation contributions to the kernel, the correlation expression decays into random-phase-approximation (RPA) -like and screened-exchange-like parts. The actual treatment of the screened potential
W in the BSE for
L leads to different second-order screened exchange corrections (SOSEX). Including correlation in the kernel even yields approximations beyond SOSEX. The progress beyond RPA is illustrated for spinless and spin-polarized homogeneous electron gases, indicating that the screening treatment is substantial.
The helium atom is the simplest many-body electronic system provided by nature. The exact solution to the Schrödinger equation is known for helium ground and excited states, and it represents a benchmark for any many-body methodology. Here, we check the ab initio many-body GW approximation and the Bethe-Salpeter equation (BSE) against the exact solution for helium. Starting from the Hartree-Fock method, we show that the GW and the BSE yield impressively accurate results on excitation energies and oscillator strength, systematically improving the time-dependent Hartree-Fock method. These findings suggest that the accuracy of the BSE and GW approximations is not significantly limited by self-interaction and self-screening problems even in this few electron limit. We further discuss our results in comparison to those obtained by time-dependent density-functional theory.