Ground and Excited State First-Order Properties in Many-Body Expanded Full Configuration Interaction Theory
arXiv:2008.03610 · doi:10.1063/5.0024791
Abstract
The recently proposed many-body expanded full configuration interaction (MBE-FCI) method is extended to excited states and static first-order properties different from total, ground state correlation energies. Results are presented for excitation energies and (transition) dipole moments of two prototypical, heteronuclear diatomics---LiH and MgO---in augmented correlation consistent basis sets of up to quadruple- quality. Given that MBE-FCI properties are evaluated without recourse to a sampled wave function and the storage of corresponding reduced density matrices, the memory overhead associated with the calculation of general first-order properties only scales with the dimension of the desired property. In combination with the demonstrated performance, the present developments are bound to admit a wide range of future applications by means of many-body expanded treatments of electron correlation.
arXiv comment22 pages, 2 figures, 2 tables. SI added as ancillary file
References in corpus (34)
- Recent developments in the PySCF program package
- Ab Initio Quantum Chemistry using the Density Matrix Renormalization Group
- Heat-bath Configuration Interaction: An efficient selected CI algorithm inspired by heat-bath sampling
- Semistochastic Heat-bath Configuration Interaction method: selected configuration interaction with semistochastic perturbation theory
- A Mountaineering Strategy to Excited States: Highly-Accurate Reference Energies and Benchmarks
- A deterministic alternative to the full configuration interaction quantum Monte Carlo method
- How accurate is density functional theory at predicting dipole moments? An assessment using a new database of 200 benchmark values
- A spin-adapted Density Matrix Renormalization Group algorithm for quantum chemistry
- An adaptive configuration interaction approach for strongly correlated electrons with tunable accuracy
- A Mountaineering Strategy to Excited States: Highly-Accurate Energies and Benchmarks for Medium Size Molecules
- Modern Approaches to Exact Diagonalization and Selected Configuration Interaction with the Adaptive Sampling CI Method
- Semistochastic Projector Monte Carlo Method
- Reference Energies for Double Excitations
- The Quest For Highly Accurate Excitation Energies: A Computational Perspective
- Pushing Configuration-Interaction to the Limit: Towards Massively Parallel MCSCF Calculations
- The Ground State Electronic Energy of Benzene
- Excited states using semistochastic heat-bath configuration interaction
- Fast Semistochastic Heat-Bath Configuration Interaction
- Unbiased Reduced Density Matrices and Electronic Properties from Full Configuration Interaction Quantum Monte Carlo
- Excited States of Methylene, Polyenes, and Ozone from Heat-Bath Configuration Interaction
- Selected configuration interaction dressed by perturbation
- Machine Learning Configuration Interaction
- Efficient heat-bath sampling in Fock space
- Virtual orbital many-body expansions: A possible route towards the full configuration interaction limit
- Many-Body Expanded Full Configuration Interaction. I. Weakly Correlated Regime
- Many-Body Expanded Full Configuration Interaction. II. Strongly Correlated Regime
- Density matrices in full configuration interaction quantum Monte Carlo: Excited states, transition dipole moments and parallel distribution
- An explicitly correlated approach to basis set incompleteness in Full Configuration Interaction Quantum Monte Carlo
- Full Coupled-Cluster Reduction for Accurate Description of Strong Electron Correlation
- Coordinate descent full configuration interaction
- Generalized Many-Body Expanded Full Configuration Interaction Theory
- Analytic nuclear forces and molecular properties from full configuration interaction quantum Monte Carlo
- Hellman-Feynman operator sampling in Diffusion Monte Carlo calculations
- An efficient deterministic perturbation theory for selected configuration interaction methods
Cited by in corpus (7)
- QUESTDB: a database of highly-accurate excitation energies for the electronic structure community
- The Shape of Full Configuration Interaction to Come
- A Mountaineering Strategy to Excited States: Highly-Accurate Oscillator Strengths and Dipole Moments of Small Molecules
- Ground- and Excited-State Dipole Moments and Oscillator Strengths of Full Configuration Interaction Quality
- Incremental Treatments of the Full Configuration Interaction Problem
- Cluster many-body expansion: a many-body expansion of the electron correlation energy about a cluster mean-field reference
- MBE-CASSCF Approach for the Accurate Treatment of Large Active Spaces