The coupled cluster method (CCM) is a powerful and widely applied technique of modern-day quantum many-body theory. It has been used with great success in order to understand the properties of quantum magnets at zero temperature. This is due largely to the application of computational techniques that allow the method to be applied to high orders of approximation using localised approximation schemes, e.g., such as the LSUB$m$ scheme. In this article, the high-order CCM formalism for the ground and excited states of quantum magnetic systems are extended to those with spin quantum number $s \ge \frac 12$. Solution strategies for the ket- and bra-state equations are also considered. Aspects of extrapolation of CCM expectation values are discussed and future topics regarding extrapolations are presented.
High-Order Coupled Cluster Method Calculations using Three-Dimensional Model States: An Illustration for the Triangular-Lattice Antiferromagnet in an External Field
The zero-temperature quantum phase diagram of the spin-$\frac{1}{2}$ $J_{1}$--$J_{2}$--$J_{1}^{\perp}$ model on an $AA$-stacked bilayer honeycomb lattice is investigated using the coupled cluster method (CCM). The model comprises two monolayers in each of which the spins, residing on honeycomb-lattice sites, interact via both nearest-neighbor (NN) and frustrating next-nearest-neighbor isotropic antiferromagnetic (AFM) Heisenberg exchange iteractions, with respective strengths $J_{1} > 0$ and $J_{2} \equiv κJ_{1}>0$. The two layers are coupled via a comparable Heisenberg exchange interaction be…
The accurate description of doubly-excited states using conventional electronic structure methods is remarkably challenging, primarily because such excited states require the inclusion of doubly or higher excited configurations or the application of multi-reference methods. We present a new approach to target electronically excited states that feature a double-electron transfer. Our method uses the equation of motion (EOM) formalism with a pair coupled cluster doubles (pCCD) reference function, where dynamical correlation is accounted for by a linearized coupled cluster correction with singles…
Like adiabatic time-dependent density-functional theory (TD-DFT), the Bethe-Salpeter equation (BSE) formalism of many-body perturbation theory, in its static approximation, is "blind" to double (and higher) excitations, which are ubiquitous, for example, in conjugated molecules like polyenes. Here, we apply the spin-flip \textit{ansatz} (which considers the lowest triplet state as the reference configuration instead of the singlet ground state) to the BSE formalism in order to access, in particular, double excitations. The present scheme is based on a spin-unrestricted version of the $GW$ appr…
The pair coupled cluster doubles (pCCD) method (where the excitation manifold is restricted to electron pairs) has a series of interesting features. Among others, it provides ground-state energies very close to what is obtained with doubly-occupied configuration interaction (DOCI), but with polynomial cost (compared with the exponential cost of the latter). Here, we address whether this similarity holds for excited states, by exploring the symmetric dissociation of the linear \ce{H4} molecule. When ground-state Hartree-Fock (HF) orbitals are employed, pCCD and DOCI excited-state energies do no…
In the framework of the computational determination of highly-accurate vertical excitation energies in small organic compounds, we explore the possibilities offered by the equation-of-motion formalism relying on the approximate fourth-order coupled-cluster (CC) method, CC4. We demonstrate, using an extended set of more than 200 reference values based on CC including up to quadruples excitations (CCSDTQ), that CC4 is an excellent approximation to CCSDTQ for excited states with a dominant contribution from single excitations with an average deviation as small as $0.003$ eV. We next assess the ac…
