Assessing the accuracy of the Jastrow antisymmetrized geminal power in the H 4 model system
| Autor: | Claudio Genovese, Sandro Sorella, Antonella Meninno |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Physics
Chemical Physics (physics.chem-ph) Physics and Astronomy (all) Physical and Theoretical Chemistry 010304 chemical physics Geminal Quantum Monte Carlo Monte Carlo method General Physics and Astronomy FOS: Physical sciences 010402 general chemistry 01 natural sciences 0104 chemical sciences Settore FIS/03 - Fisica della Materia Physics - Chemical Physics 0103 physical sciences Convergence (routing) Diffusion Monte Carlo Statistical physics Ground state Basis set Ansatz |
| Popis: | 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. Comment: Accepted on Journal of Chemical Physics |
| Databáze: | OpenAIRE |
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