Strong electron correlations in electronic structure theory are purely quantum effects arising as a result of degeneracies in molecules and materials, and exhibit significantly different yet interesting characters than do weak correlations. Although weak correlations have recently been able to be described very efficiently and accurately within single particle pictures, less known are good prescriptions for treating strong correlations efficiently. Brute-force calculations of strong correlations in wave function theories tend to be very computationally-intensive, and are usually limited to small molecules for applications. Breaking symmetry in a mean-field approximation is an efficient alternative to acquire strong correlations with, in many cases, qualitatively accurate results. The symmetry broken in quantum chemistry has been traditionally of spin, in so-called unrestricted methods, which typically break spatial symmetry as a consequence, and vice versa, in most situations. In this work, we present a novel approach to accurately describing strong correlations with a mean-field cost by means of Hartree- Fock-Bogoliubov (HFB) theory. We are inspired by the number-symmetry-breaking in HFB, which, with an attractive particle interaction, accounts for strong correlations, while maintaining spin and spatial symmetry. We show that this attractive interaction must be restricted to the chemically-relevant orbitals in an active space to obtain physically meaningful results. With such constraints, our constrained pairing mean-field theory (CPMFT) can accurately describe potential energy curves of various strongly-correlated molecular systems, by cleanly separating strong and weak correlations. To achieve the correct dissociation limits in hetero-atomic molecules, we have modified our CPMFT functional by adding asymptotic constraints. We also include weak correlations by combining CPMFT with density functional theory for chemically accurate results, and reveal the connection between CPMFT and traditional unrestricted methods. The similarity between CPMFT and unrestricted methods leads us to the idea of constrained active space unrestricted mean-field approaches. Motivated by CPMFT, we partially retrieve spin-symmetry that has been fully broken in unrestricted methods. We allow symmetry breaking only in an active space. This constrained unrestricted Hartree-Fock (CUHF) is an interpolation between two extrema: the fully broken-symmetry solution and the symmetry preserved solution. This thesis defines the theory behind and reports the results of CUHF. We first show that, if an active space is chosen to include only open-shell electrons, CUHF reduces to restricted open-shell Hartree-Fock (ROHF), and such CUHF proves in many ways significantly

Motivated by our frustration with the lack of quantum chemistry methods for strongly-correlated open-shell systems, we develop quantitative methods for computing the electronic structure of such systems and qualitative tools for analyzing their chemical properties and reactivity. Specifically, we present a modern framework for performing sparse configuration interaction (CI) computations with arbitrary (Slater determinant) N-electron basis sets, using restricted or generalized spin-orbitals, and including computation of spin-polarized 1- and 2- electron reduced density matrices (RDMs). This framework is then used to implement the flexible ansätze for N-electron CI (FanCI) method more efficiently, via increased vectorization in the FanCI equations and use of sparse CI algorithms. We also extended the FanCI approach, including least-squares and stochastic optimization techniques, the computation of spin-polarized 1- and 2- electron RDMs, and transition energies (ionization potentials, electron affinities, and excitation energies). We use these tools to compare various open-shell CI methods and FanCI methods based on various antisymmetrized product of nonorthogonal geminals ansätze. To translate the vast amount of quantitative data present in the energies and (spin-polarized) density matrices of multiple open-shell states, we present a new, internally consistent and unambiguous framework for spin-polarized conceptual density-functional theory (SP-DFT) that reduces to a sensible formulation of spin-free CDFT in an appropriate limit. Using this framework, we were able to generalize the (non-spin-polarized) Parr function. We can also, using this framework, construct promolecules with proatoms having non-integer charges and multiplicities. Finally, we describe an equations-of-motion-based method for computing spin-polarized reactivity descriptors of a chemical system from only the ground state energy and the 1- and 2- electron RDMs from a single-point electronic structure computation, and show some benchmark computations for this method based on various CI and FanCI electronic structure methods. / Thesis / Doctor of Philosophy (PhD)