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Register a new userRichardson-Gaudin mean-field for strong correlation in quantum chemistry
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Ground state eigenvectors of the reduced Bardeen-Cooper-Schrieffer Hamiltonian are employed as a wavefunction ansatz to model strong electron correlation in quantum chemistry. This wavefunction is a product of weakly-interacting pairs of electrons. While other geminal wavefunctions may only be employed in a projected Schr{o}dinger equation, the present approach may be solved variationally with polynomial cost. The resulting wavefunctions are used to compute expectation values of Coulomb Hamiltionans and we present results for atoms and dissociation curves which are in agreement with doubly-occupied configuration interaction (DOCI) data. The present approach will serve as the starting point for a many-body theory of pairs, much as Hartree-Fock is the starting point for weakly-correlated electrons.
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In specific open systems with collective dissipation the Liouvillian can be mapped to a non-Hermitian Hamiltonian. We here consider such a system where the Liouvillian is mapped to an XXZ Richardson-Gaudin integrable model and detail its exact Bethe ansatz solution. While no longer Hermitian, the Hamiltonian is pseudo-Hermitian/PT-symmetric, and as the strength of the coupling to the environment is increased the spectrum in a fixed symmetry sector changes from a broken pseudo-Hermitian phase with complex conjugate eigenvalues to a pseudo-Hermitian phase with real eigenvalues, passing through a series of exceptional points and associated dissipative quantum phase transitions. The homogeneous limit supports a nontrivial steady state, and away from this limit this state gives rise to a slow logarithmic growth of the decay rate (spectral gap) with system size. Using the exact solution, it is furthermore shown how at large coupling strengths the ratio of the imaginary to the real part of the eigenvalues becomes approximately quantized in the remaining symmetry sectors.
This thesis presents an introduction to the class of Richardson-Gaudin integrable models, with special focus on the Bethe ansatz wave function, and investigates ways of applying the properties of Richardson-Gaudin models both in and out of integrability. A framework is outlined for the numerical and theoretical treatment of these systems, exposing a duality allowing the Bethe equations to be solved numerically. This is extended to the calculation of inner products and correlation functions. Using this framework, the influence of particle exchange on the Bethe ansatz is discussed, after which it is shown how the Bethe ansatz is able to accurately model wave functions of non-integrable models in two different settings. First, a variational approach is outlined for stationary models where integrability-breaking perturbations are explicitly introduced. Second, an alternative way of breaking integrability is through the introduction of dynamics and periodic driving, where it is shown how integrability can be used to model the resulting Floquet many-body resonances. Throughout this work, it is shown how the clear-cut structure and relatively large freedom in Richardson-Gaudin models makes them ideal for an investigation of the general principles of integrability, as well as being a perfect testing ground for the development of new quantum many-body techniques beyond integrability.
A full coupled-cluster expansion suitable for sparse algebraic operations is developed by expanding the commutators of the Baker-Campbell-Hausdorff series explicitly for cluster operators in binary representations. A full coupled-cluster reduction that is capable of providing very accurate solutions of the many-body Schrodinger equation is then initiated employing screenings to the projection manifold and commutator operations. The projection manifold is iteratively updated through the single commutators $leftlangle kappa right| [hat H,hat T]left| 0 rightrangle$ comprised of the primary clusters $hat T_{lambda}$ with substantial contribution to the connectivity. The operation of the commutators is further reduced by introducing a correction, taking into account the so-called exclusion principle violating terms, that provides fast and near-variational convergence in many cases.
Fanpy is a free and open-source Python library for developing and testing multideterminant wavefunctions and related ab initio methods in electronic structure theory. The main use of Fanpy is to quickly prototype new methods by making it easier to transfer the mathematical conception of a new wavefunction ans{a}tze to a working implementation. Fanpy uses the framework of our recently introduced Flexible Ansatz for N-electron Configuration Interaction (FANCI), where multideterminant wavefunctions are represented by their overlaps with Slater determinants of orthonormal spin-orbitals. In the simplest case, a new wavefunction ansatz can be implemented by simply writing a function for evaluating its overlap with an arbitrary Slater determinant. Fanpy is modular in both implementation and theory: the wavefunction model, the systems Hamiltonian, and the choice of objective function are all independent modules. This modular structure makes it easy for users to mix and match different methods and for developers to quickly try new ideas. Fanpy is written purely in Python with standard dependencies, making it accessible for most operating systems; it adheres to principles of modern software development, including comprehensive documentation, extensive testing, and continuous integration and delivery protocols. This article is considered to be the official release notes for the Fanpy library.
Reliable quantum chemical methods for the description of molecules with dense-lying frontier orbitals are needed in the context of many chemical compounds and reactions. Here, we review developments that led to our newcomputational toolbo x which implements the quantum chemical density matrix renormalization group in a second-generation algorithm. We present an overview of the different components of this toolbox.
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