We report a quantum Monte Carlo study, on a very simple but nevertheless very instructive model system of four hydrogen atoms, recently proposed in Gasperich et al. [J. Chem. Phys. 147, 074106 (2017)]. 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, which 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, when the so called diffusion Monte Carlo is applied.

Assessing the accuracy of the Jastrow antisymmetrized geminal power in the H 4 model system / Genovese, C.; Meninno, A.; Sorella, S.. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 150:8(2019), pp. 1-7. [10.1063/1.5081933]

Assessing the accuracy of the Jastrow antisymmetrized geminal power in the H 4 model system

Genovese, C.
Membro del Collaboration group
;
Meninno, A.
Membro del Collaboration group
;
Sorella, S.
Membro del Collaboration group
2019

Abstract

We report a quantum Monte Carlo study, on a very simple but nevertheless very instructive model system of four hydrogen atoms, recently proposed in Gasperich et al. [J. Chem. Phys. 147, 074106 (2017)]. 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, which 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, when the so called diffusion Monte Carlo is applied.
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https://aip.scitation.org/doi/10.1063/1.5081933
Genovese, C.; Meninno, A.; Sorella, S.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/20.500.11767/87971
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