Cluster many-body expansion: a many-body expansion of the electron correlation energy about a cluster mean-field reference
arXiv:2105.10548 · doi:10.1063/5.0057752
Abstract
The many-body expansion (MBE) is an efficient tool which has a long history of use for calculating interaction energies, binding energies, lattice energies, and so on. In the past, applications of MBE to correlation energy have been unfeasible for large systems, but recent improvements to computing resources have sparked renewed interest in capturing the correlation energy using the generalized -th order Bethe-Goldstone equation. In this work, we extend this approach, originally proposed for a Slater determinant, to a tensor product state (TPS) based wavefunction. By partitioning the active space into smaller orbital clusters, our approach starts from a cluster mean field reference TPS configuration and includes the correlation contribution of the excited TPSs using the many-body expansion. This method, named cluster many-body expansion (cMBE), improves the convergence of MBE at lower orders compared to directly doing a block based MBE from a RHF reference. We present numerical results for strongly correlated systems such as the one- and two-dimensional Hubbard models and the chromium dimer. The performance of the cMBE method is also tested by partitioning the extended space of several large -conjugated systems, including a graphene nano-sheet with a very large active space of 114 electrons in 114 orbitals, which would require determinants for the exact FCI solution.
References in corpus (33)
- Recent developments in the PySCF program package
- The ITensor Software Library for Tensor Network Calculations
- Ab Initio Quantum Chemistry using the Density Matrix Renormalization Group
- Heat-bath Configuration Interaction: An efficient selected CI algorithm inspired by heat-bath sampling
- The radical character of the acenes: A density matrix renormalization group study
- A deterministic alternative to the full configuration interaction quantum Monte Carlo method
- Low-energy spectrum of iron-sulfur clusters directly from many-particle quantum mechanics
- An adaptive configuration interaction approach for strongly correlated electrons with tunable accuracy
- Efficient Tree Tensor Network States (TTNS) for Quantum Chemistry: Generalizations of the Density Matrix Renormalization Group Algorithm
- The Ground State Electronic Energy of Benzene
- Fast Semistochastic Heat-Bath Configuration Interaction
- Hybrid stochastic-deterministic calculation of the second-order perturbative contribution of multireference perturbation theory
- Linear-scaling and parallelizable algorithms for stochastic quantum chemistry
- Electronic landscape of the P-cluster of nitrogenase as revealed through many-electron quantum wavefunctions
- Complete-Graph Tensor Network States: A New Fermionic Wave Function Ansatz for Molecules
- Virtual orbital many-body expansions: A possible route towards the full configuration interaction limit
- Role of Kekulé and Non-Kekulé Structures in the Radical Character of Alternant Polycyclic Aromatic Hydrocarbons: A TAO-DFT Study
- Selected Configuration Interaction in a Basis of Cluster State Tensor Products
- Active space decomposition with multiple sites: Density matrix renormalization group algorithm
- Many-Body Expanded Full Configuration Interaction. I. Weakly Correlated Regime
- Many-Body Expanded Full Configuration Interaction. II. Strongly Correlated Regime
- A cluster-based mean-field and perturbative description of strongly correlated fermion systems. Application to the 1D and 2D Hubbard model
- Full Coupled-Cluster Reduction for Accurate Description of Strong Electron Correlation
- Coordinate descent full configuration interaction
- Generalized Many-Body Expanded Full Configuration Interaction Theory
- Accurate many-body electronic structure near the basis set limit: application to the chromium dimer
- Scaling Up Electronic Structure Calculations on Quantum Computers: The Frozen Natural Orbital Based Method of Increments
- Making Many-Body Interactions Nearly Pairwise Additive: The Polarized Many-Body Expansion Approach
- Cluster decomposition of full configuration interaction wave functions: a tool for chemical interpretation of systems with strong correlation
- A renormalized excitonic method in terms of block excitations. Application to spin lattices
- Ground and Excited State First-Order Properties in Many-Body Expanded Full Configuration Interaction Theory
- Excitonic Coupled-cluster Theory
- Incremental expansions for the ground state energy of the two-dimensional Hubbard model