Orbital Optimization in Selected Configuration Interaction Methods

Abstract

We study several approaches to orbital optimization in selected configuration interaction plus perturbation theory (SCI+PT) methods, and test them on the ground and excited states of three molecules using the semistochastic heatbath configuration interaction (SHCI) method. We discuss the ways in which the orbital optimization problem in SCI resembles and differs from that in complete active space self-consistent field (CASSCF). Starting from natural orbitals, these approaches divide into three classes of optimization methods according to how they treat coupling between configuration interaction (CI) coefficients and orbital parameters, namely uncoupled, fully coupled, and quasi-fully coupled methods. We demonstrate that taking the coupling into account is crucial for fast convergence and recommend two quasi-fully coupled methods for such applications: accelerated diagonal Newton and Broyden-Fletcher-Goldfarb-Shanno (BFGS).

arXiv comment5 figures

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• Density Matrices of Seniority-Zero Geminal Wavefunctions
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• Second-order self-consistent field algorithms: from classical to quantum nuclei
• Reference Vertical Excitation Energies for Transition Metal Compounds
• Improved Optimization for the Neural-network Quantum States and Tests on the Chromium Dimer
• Accurate energies of transition metal atoms, ions, and monoxides using selected configuration interaction and density-based basis-set corrections
• MBE-CASSCF Approach for the Accurate Treatment of Large Active Spaces
• Rationale for the Extrapolation Procedure in Selected Configuration Interaction
• Economical Quasi-Newton Self Consistent Field Solver
• Selected Configuration Interaction for Resonances
• Orthogonally Constrained Orbital Optimization: assessing changes of optimal orbitals for orthogonal multi-reference states
• Direct determination of optimal real-space orbitals for correlated electronic structure of molecules
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• Near-exact treatment of seniority-zero ground and excited states with a Richardson-Gaudin mean-field
• iCISCF: An Iterative Configuration Interaction-based Multiconfigurational Self-consistent Field Theory for Large Active Spaces
• $i$CAS: Imposed Automatic Selection and Localization of Complete Active Spaces
• Near-Exact Nuclear Gradients of Complete Active Space Self-Consistent Field Wave Functions