Optimal Orbital Selection for Full Configuration Interaction (OptOrbFCI): Pursuing the Basis Set Limit under a Budget

Abstract

Full configuration interaction (FCI) solvers are limited to small basis sets due to their expensive computational costs. An optimal orbital selection for FCI (OptOrbFCI) is proposed to boost the power of existing FCI solvers to pursue the basis set limit under a computational budget. The optimization problem coincides with that of the complete active space SCF method (CASSCF), while OptOrbFCI is algorithmically quite different. OptOrbFCI effectively finds an optimal rotation matrix via solving a constrained optimization problem directly to compress the orbitals of large basis sets to one with a manageable size, conducts FCI calculations only on rotated orbital sets, and produces a variational ground-state energy and its wave function. Coupled with coordinate descent full configuration interaction (CDFCI), we demonstrate the efficiency and accuracy of the method on the carbon dimer and nitrogen dimer under basis sets up to cc-pV5Z. We also benchmark the binding curve of the nitrogen dimer under the cc-pVQZ basis set with 28 selected orbitals, which provide consistently lower ground-state energies than the FCI results under the cc-pVDZ basis set. The dissociation energy in this case is found to be of higher accuracy.

References in corpus (28)

• Heat-bath Configuration Interaction: An efficient selected CI algorithm inspired by heat-bath sampling
• Quantum Simulation of Electronic Structure with Linear Depth and Connectivity
• Semistochastic Heat-bath Configuration Interaction method: selected configuration interaction with semistochastic perturbation theory
• Orbital Optimization in the Density Matrix Renormalization Group, with applications to polyenes and β-carotene
• A deterministic alternative to the full configuration interaction quantum Monte Carlo method
• An adaptive configuration interaction approach for strongly correlated electrons with tunable accuracy
• Cheap and near exact CASSCF with large active spaces
• Modern Approaches to Exact Diagonalization and Selected Configuration Interaction with the Adaptive Sampling CI Method
• Semistochastic Projector Monte Carlo Method
• CASSCF with Extremely Large Active Spaces using the Adaptive Sampling Configuration Interaction Method
• A general second order complete active space self-consistent-field solver for large-scale systems
• Understanding the mechanism stabilizing intermediate spin states in Fe(II)-Porphyrin
• Multi-reference perturbation theory with Cholesky decomposition for the density matrix renormalization group
• DMRG-SCF study of the singlet, triplet, and quintet states of oxo-Mn(Salen)
• Quantum Simulation of Chemistry with Sublinear Scaling in Basis Size
• Second-Order Self-Consistent-Field Density-Matrix Renormalization Group
• Parallelizable Algorithms for Optimization Problems with Orthogonality Constraints
• A Primer on Coordinate Descent Algorithms
• Coordinate descent full configuration interaction
• Are natural orbitals useful for generating an efficient expansion of the wave function?
• Approximate analytical gradients and nonadiabatic couplings for the state-average density matrix renormalization group self-consistent field method
• Fast randomized iteration: diffusion Monte Carlo through the lens of numerical linear algebra
• Coordinate-wise descent methods for leading eigenvalue problem
• Optimal multi-configuration approximation of an N-fermion wave function
• The full configuration interaction quantum Monte Carlo method in the lens of inexact power iteration
• A greedy algorithm for computing eigenvalues of a symmetric matrix
• Beyond Walkers in Stochastic Quantum Chemistry: Reducing Error using Fast Randomized Iteration
• Triangularized Orthogonalization-free Method for Solving Extreme Eigenvalue Problems

Cited by in corpus (4)

• The Shape of Full Configuration Interaction to Come
• Benchmarking the Variational Quantum Eigensolver through Simulation of the Ground State Energy of Prebiotic Molecules on High-Performance Computers
• Triangularized Orthogonalization-free Method for Solving Extreme Eigenvalue Problems
• A Finite Element Configuration Interaction Method for Wigner Localization