We report the development of a python-based auxiliary-field quantum Monte Carlo (AFQMC) program, ipie, with preliminary timing benchmarks and new AFQMC results on the isomerization of [Cu 2 O 2 ] 2+ . We demonstrate how implementations for both central and graphical processing units (CPUs and GPUs) are achieved in ipie . We show an interface of ipie with PySCF as well as a straightforward template for adding new estimators to ipie . Our timing benchmarks against other C++ codes, QMCPACK and Dice, suggest that ipie is faster or similarly performing for all chemical systems considered on both CPUs and GPUs. Our results on [Cu 2 O 2 ] 2+ using selected configuration interaction trials show that it is possible to converge the ph-AFQMC isomerization energy between bis(μ-oxo) and μ-η 2:η 2 peroxo configurations to the exact known results for small basis sets with 10 5 –10 6 determinants. We also report the isomerization energy with a quadruple-zeta basis set with an estimated error less than a kcal/mol, which involved 52 electrons and 290 orbitals with 10 6 determinants in the trial wave function. These results highlight the utility of ph-AFQMC and ipie for systems with modest strong correlation and large-scale dynamic correlation.
We report the development of a python-based auxiliary-field quantum Monte Carlo (AFQMC) program, ipie, with preliminary timing benchmarks and new AFQMC results on the isomerization of [Cu 2 O 2 ] 2+ . We demonstrate how implementations for both central and graphical processing units (CPUs and GPUs) are achieved in ipie . We show an interface of ipie with PySCF as well as a straightforward template for adding new estimators to ipie . Our timing benchmarks against other C++ codes, QMCPACK and Dice, suggest that ipie is faster or similarly performing for all chemical systems considered on both CPUs and GPUs. Our results on [Cu 2 O 2 ] 2+ using selected configuration interaction trials show that it is possible to converge the ph-AFQMC isomerization energy between bis(μ-oxo) and μ-η 2:η 2 peroxo configurations to the exact known results for small basis sets with 10 5 –10 6 determinants. We also report the isomerization energy with a quadruple-zeta basis set with an estimated error less than a kcal/mol, which involved 52 electrons and 290 orbitals with 10 6 determinants in the trial wave function. These results highlight the utility of ph-AFQMC and ipie for systems with modest strong correlation and large-scale dynamic correlation.
ipie is a Python-based auxiliary-field quantum Monte Carlo (AFQMC) package that has undergone substantial improvements since its initial release [Malone et al., J. Chem. Theory Comput. 19(1), 109-121 (2023)]. This paper outlines the improved modularity and new capabilities implemented in ipie. We highlight the ease of incorporating different trial and walker types and the seamless integration of ipie with external libraries. We enable distributed Hamiltonian simulations of large systems that otherwise would not fit on a single central processing unit node or graphics processing unit (GPU) card. This development enabled us to compute the interaction energy of a benzene dimer with 84 electrons and 1512 orbitals with multi-GPUs. Using CUDA and cupy for NVIDIA GPUs, ipie supports GPU-accelerated multi-slater determinant trial wavefunctions [Huang et al. arXiv:2406.08314 (2024)] to enable efficient and highly accurate simulations of large-scale systems. This allows for near-exact ground state energies of multi-reference clusters, [Cu2O2]2+ and [Fe2S2(SCH3)4]2-. We also describe implementations of free projection AFQMC, finite temperature AFQMC, AFQMC for electron-phonon systems, and automatic differentiation in AFQMC for calculating physical properties. These advancements position ipie as a leading platform for AFQMC research in quantum chemistry, facilitating more complex and ambitious computational method development and their applications.
Phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) has recently emerged as a promising method for the production of benchmark-level simulations of medium- to large-sized molecules because of its accuracy and favorable polynomial scaling with system size. Unfortunately, the memory footprints of standard energy evaluation algorithms are nontrivial, which can significantly impact timings on graphical processing units (GPUs) where memory is limited. Previous attempts to reduce scaling by taking advantage of the low-rank structure of the Coulombic integrals have been successful but exhibit high prefactors, making their utility limited to very large systems. Here we present a complementary cubic-scaling route to reduce memory and computational scaling based on the low rank of the Coulombic interactions between localized orbitals, focusing on the application to ph-AFQMC. We show that the error due to this approximation, which we term localized-orbital AFQMC (LO-AFQMC), is systematic and controllable via a single variable and that the method is computationally favorable even for small systems. We present results demonstrating robust retention of accuracy versus both experiment and full ph-AFQMC for a variety of test cases chosen for their potential difficulty for localized-orbital-based methods, including the singlet–triplet gaps of the polyacenes benzene through pentacene, the heats of formation for a set of Platonic hydrocarbon cages, and the total energy of ferrocene, Fe(Cp) 2 . Finally, we reproduce our previous result for the gas-phase ionization energy of Ni(Cp) 2, agreeing with full ph-AFQMC to within statistical error while using less than 1/15th of the computer time.
The phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) method is a stochastic imaginary-time projection method for computing ground-state properties of strongly correlated quantum systems, whose accuracy depends critically on the trial wavefunction. We present a benchmarking study of trial wavefunctions prepared using parameterized quantum circuits, spanning unitary coupled cluster (UCC), Hamiltonian-informed, Jastrow-inspired, and adaptively constructed ansatzes, and evaluate their accuracy, expressibility, and resource requirements within the quantum-computing-enhanced AFQMC (QC-AFQMC) framework. Trial states are prepared with GPU-accelerated statevector simulations using CUDA-Q and tested on stretched linear hydrogen chains and nine closed-shell molecules at equilibrium with varying static correlation. We find that at similar parameter counts, ph-AFQMC largely removes differences between families for weakly and moderately correlated systems: every trial yields a ph-AFQMC energy within chemical accuracy despite trial energy errors spanning nearly three orders of magnitude, whereas ansatz choice becomes consequential as static correlation grows. Our results indicate that trial variational energy is not always a reliable indicator of ph-AFQMC quality, and that adding variational parameters can lower the trial energy while degrading the ph-AFQMC energy. Across our benchmark systems, trial fidelity ranks trials more reliably than variational energy, and for spin-contaminated trials, the singlet-projected fidelity is more reliable than unprojected fidelity. The UCCSD ansatz initialized from unrestricted CCSD amplitudes provides a robust and inexpensive-to-optimize baseline across benchmark systems, with circuit depth as its principal limitation, while adaptive and compact layered ansatzes remain competitive in accuracy under strong correlation with substantially shallower circuits.
High Resolution Image Download MS PowerPoint Slide We report a scalable Fortran implementation of the phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) and demonstrate its excellent performance and beneficial scaling with respect to system size. Furthermore, we investigate modifications of the phaseless approximation that can help to reduce the overcorrelation problems common to the ph-AFQMC. We apply the method to the 26 molecules in the HEAT set, the benzene molecule, and water clusters. We observe a mean absolute deviation of the total energy of 1.15 kcal/mol for the molecules in the HEAT set, close to chemical accuracy. For the benzene molecule, the modified algorithm despite using a single-Slater-determinant trial wavefunction yields the same accuracy as the original phaseless scheme with 400 Slater determinants. Despite these improvements, we find systematic errors for the CN, CO 2, and O 2 molecules that need to be addressed with more accurate trial wavefunctions. For water clusters, we find that the ph-AFQMC yields excellent binding energies that differ from CCSD(T) by typically less than 0.5 kcal/mol.
We review recent advances in the capabilities of the open source ab initio Quantum Monte Carlo (QMC) package QMCPACK and the workflow tool Nexus used for greater efficiency and reproducibility. The auxiliary field QMC (AFQMC) implementation has been greatly expanded to include k-point symmetries, tensor-hypercontraction, and accelerated graphical processing unit (GPU) support. These scaling and memory reductions greatly increase the number of orbitals that can practically be included in AFQMC calculations, increasing the accuracy. Advances in real space methods include techniques for accurate computation of bandgaps and for systematically improving the nodal surface of ground state wavefunctions. Results of these calculations can be used to validate application of more approximate electronic structure methods, including GW and density functional based techniques. To provide an improved foundation for these calculations, we utilize a new set of correlation-consistent effective core potentials (pseudopotentials) that are more accurate than previous sets; these can also be applied in quantum-chemical and other many-body applications, not only QMC. These advances increase the efficiency, accuracy, and range of properties that can be studied in both molecules and materials with QMC and QMCPACK.