Assessing the Accuracy of the Jastrow Antisymmetrized Geminal Power in the H4 Model System
arXiv:1905.06971 · doi:10.1063/1.5081933
Abstract
We report a quantum Monte Carlo (QMC) study, on a very simple but nevertheless very instructive model system of four hydrogen atoms, recently proposed in Ref. 1. We find that the Jastrow correlated Antisymmetrized Geminal Power (JAGP) is able to recover most of the correlation energy even when the geometry is symmetric and the hydrogens lie on the edges of a perfect square. Under such conditions the diradical character of the molecule ground state prevents a single determinant ansatz to achieve an acceptable accuracy, whereas the JAGP performs very well for all geometries. Remarkably, this is obtained with a similar computational effort. Moreover we find that the Jastrow Factor is fundamental in promoting the correct resonances among several configurations in the JAGP, that cannot show up in the pure Antisymmetrized Geminal Power (AGP). We also show the extremely fast convergence of this approach in the extension of the basis set. Remarkably only the simultaneous optimization of the Jastrow and the AGP part of our variational ansatz is able to recover an almost perfect nodal surface, yielding therefore state of the art energies, almost converged in the complete basis set limit (CBS), when the so called Diffusion Monte Carlo is applied.
arXiv commentAccepted on Journal of Chemical Physics
References in corpus (16)
- Generalized Lanczos Algorithm for Variational Quantum Monte Carlo
- Towards the solution of the many-electron problem in real materials: equation of state of the hydrogen chain with state-of-the-art many-body methods
- Correlated geminal wave function for molecules: an efficient resonating valence bond approach
- Applications of quantum Monte Carlo methods in condensed systems
- Geminal wavefunctions with Jastrow correlation: a first application to atoms
- Pfaffian pairing wave functions in electronic structure quantum Monte Carlo
- Size-consistent variational approaches to non-local pseudopotentials: standard and lattice regularized diffusion Monte Carlo methods revisited
- Multi-Determinant Wave-functions in Quantum Monte Carlo
- Pfaffian pairing and backflow wave functions for electronic structure quantum Monte Carlo methods
- Algorithmic differentiation and the calculation of forces by quantum Monte Carlo
- An exactly size consistent geminal power via Jastrow factor networks in a local one particle basis
- Resonating valence bond wave function with molecular orbitals: Application to first-row molecules
- Strong electronic correlation in the Hydrogen chain: a variational Monte Carlo study
- The Jastrow antisymmetric geminal power in Hilbert space: theory, benchmarking, and application to a novel transition state
- A Jastrow factor coupled cluster theory for weak and strong electron correlation
- Quantum Monte Carlo with Variable Spins
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- Beyond single-reference fixed-node approximation in ab initio Diffusion Monte Carlo using antisymmetrized geminal power applied to systems with hundreds of electrons
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