Hilbert space multireference coupled clusters tailored by matrix product states
arXiv:2304.01625 · doi:10.1063/5.0174461
Abstract
The DMRG method, despite its favorable scaling, it is in practice not suitable for computations of dynamic correlation. Several approaches to include that in post-DMRG methods exist; in our group we focused on the tailored-CC (TCC) approach. This method works well in many situations, however, in exactly degenerate cases (with two or more determinants of equal weight), it exhibits a bias towards the reference determinant representing the Fermi vacuum. Although in some cases it is possible to use a compensation scheme to avoid this bias for energy differences, as we did in a previous work on the singlet-triplet gap in the tetramethylenethane (TME) molecule, it is certainly a drawback. In order to overcome the single-reference bias of the TCC method, we have developed a Hilbert-space multireference version of tailored CC, which can treat several determinants on an equal footing. We have employed a multireference analysis of the DMRG wave function in the matrix product state form to get the active amplitudes for each reference determinant and their constant contribution to the effective Hamiltonian. We have implemented and compared the performance of three Hilbert-space MRCC variants - the state universal one, and the Brillouin-Wigner and Mukherjee's state specific ones. We have assessed these approaches on the cyclobutadiene and tetramethylenethane (TME) molecules, which are both diradicals with exactly degenerate determinants at a certain geometry. Two DMRG active spaces have been selected based on orbital entropies, while the MRCC active space comprised the HOMO and LUMO orbitals needed for description of the diradical. We have also investigated the sensitivity of the results on orbital rotation of the HOMO-LUMO pair, as it is well known that Hilbert-space MRCC methods are not invariant to such transformations.
References in corpus (27)
- The density-matrix renormalization group in the age of matrix product states
- The density-matrix renormalization group
- Thermodynamic limit of the density matrix renormalization for the spin-1 Heisenberg chain
- Ab Initio Quantum Chemistry using the Density Matrix Renormalization Group
- The Density Matrix Renormalization Group in Chemistry and Molecular Physics: Recent Developments and New Challenges
- The density matrix renormalization group for ab initio quantum chemistry
- Tensor product methods and entanglement optimization for ab initio quantum chemistry
- Controlling the accuracy of the density matrix renormalization group method: The Dynamical Block State Selection approach
- Semistochastic Projector Monte Carlo Method
- Quantum data compression, quantum information generation, and the density-matrix renormalization group method
- A canonical transformation theory from extended normal ordering
- Unbiased Reduced Density Matrices and Electronic Properties from Full Configuration Interaction Quantum Monte Carlo
- Multi-reference perturbation theory with Cholesky decomposition for the density matrix renormalization group
- A flexible multi-reference perturbation theory by minimizing the Hylleraas functional with matrix product states
- Coupled cluster method with single and double excitations tailored by matrix product state wave functions
- Construction of CASCI-type wave functions for very large active spaces
- Time-dependent N-electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes
- The Thouless theorem for matrix product states and subsequent post-density matrix renormalization group methods
- Full configuration interaction quantum Monte Carlo benchmark and multireference coupled cluster studies of tetramethyleneethane diradical
- Tailored Coupled Cluster Theory in Varying Correlation Regimes
- Towards DMRG-tailored coupled cluster method in the 4c-relativistic domain
- Near-linear Scaling in DMRG-based Tailored Coupled Clusters: An Implementation of DLPNO-TCCSD and DLPNO-TCCSD(T)
- Towards the Efficient Local Tailored Coupled Cluster Approximation and the Peculiar Case of Oxo-Mn(Salen)
- High-Level Coupled-Cluster Energetics by Monte Carlo Sampling and Moment Expansions: Further Details and Comparisons
- Towards large-scale restricted active space calculations inspired by the Schmidt decomposition
- Toward more accurate adiabatic connection approach for multireference wave functions
- Converging High-Level Coupled-Cluster Energetics via Adaptive Selection of Excitation Manifolds Driven by Moment Expansions