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Perturbatively Selected Configuration-Interaction Wave Functions for Efficient Geometry Optimization in Quantum Monte Carlo
[Image: see text] We investigate the performance of a class of compact and systematically improvable Jastrow–Slater wave functions for the efficient and accurate computation of structural properties, where the determinantal component is expanded with a perturbatively selected configuration interacti...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2018
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6096455/ https://www.ncbi.nlm.nih.gov/pubmed/29953810 http://dx.doi.org/10.1021/acs.jctc.8b00393 |
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author | Dash, Monika Moroni, Saverio Scemama, Anthony Filippi, Claudia |
author_facet | Dash, Monika Moroni, Saverio Scemama, Anthony Filippi, Claudia |
author_sort | Dash, Monika |
collection | PubMed |
description | [Image: see text] We investigate the performance of a class of compact and systematically improvable Jastrow–Slater wave functions for the efficient and accurate computation of structural properties, where the determinantal component is expanded with a perturbatively selected configuration interaction scheme (CIPSI). We concurrently optimize the molecular ground-state geometry and full wave function—Jastrow factor, orbitals, and configuration interaction coefficients—in variational Monte Carlo (VMC) for the prototypical case of 1,3-trans-butadiene, a small yet theoretically challenging π-conjugated system. We find that the CIPSI selection outperforms the conventional scheme of correlating orbitals within active spaces chosen by chemical intuition: it gives significantly better variational and diffusion Monte Carlo energies for all but the smallest expansions, and much smoother convergence of the geometry with the number of determinants. In particular, the optimal bond lengths and bond-length alternation of butadiene are converged to better than 1 mÅ with just a few thousand determinants, to values very close to the corresponding CCSD(T) results. The combination of CIPSI expansion and VMC optimization represents an affordable tool for the determination of accurate ground-state geometries in quantum Monte Carlo. |
format | Online Article Text |
id | pubmed-6096455 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-60964552018-08-20 Perturbatively Selected Configuration-Interaction Wave Functions for Efficient Geometry Optimization in Quantum Monte Carlo Dash, Monika Moroni, Saverio Scemama, Anthony Filippi, Claudia J Chem Theory Comput [Image: see text] We investigate the performance of a class of compact and systematically improvable Jastrow–Slater wave functions for the efficient and accurate computation of structural properties, where the determinantal component is expanded with a perturbatively selected configuration interaction scheme (CIPSI). We concurrently optimize the molecular ground-state geometry and full wave function—Jastrow factor, orbitals, and configuration interaction coefficients—in variational Monte Carlo (VMC) for the prototypical case of 1,3-trans-butadiene, a small yet theoretically challenging π-conjugated system. We find that the CIPSI selection outperforms the conventional scheme of correlating orbitals within active spaces chosen by chemical intuition: it gives significantly better variational and diffusion Monte Carlo energies for all but the smallest expansions, and much smoother convergence of the geometry with the number of determinants. In particular, the optimal bond lengths and bond-length alternation of butadiene are converged to better than 1 mÅ with just a few thousand determinants, to values very close to the corresponding CCSD(T) results. The combination of CIPSI expansion and VMC optimization represents an affordable tool for the determination of accurate ground-state geometries in quantum Monte Carlo. American Chemical Society 2018-06-28 2018-08-14 /pmc/articles/PMC6096455/ /pubmed/29953810 http://dx.doi.org/10.1021/acs.jctc.8b00393 Text en Copyright © 2018 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes. |
spellingShingle | Dash, Monika Moroni, Saverio Scemama, Anthony Filippi, Claudia Perturbatively Selected Configuration-Interaction Wave Functions for Efficient Geometry Optimization in Quantum Monte Carlo |
title | Perturbatively Selected Configuration-Interaction
Wave Functions for Efficient Geometry Optimization in Quantum Monte
Carlo |
title_full | Perturbatively Selected Configuration-Interaction
Wave Functions for Efficient Geometry Optimization in Quantum Monte
Carlo |
title_fullStr | Perturbatively Selected Configuration-Interaction
Wave Functions for Efficient Geometry Optimization in Quantum Monte
Carlo |
title_full_unstemmed | Perturbatively Selected Configuration-Interaction
Wave Functions for Efficient Geometry Optimization in Quantum Monte
Carlo |
title_short | Perturbatively Selected Configuration-Interaction
Wave Functions for Efficient Geometry Optimization in Quantum Monte
Carlo |
title_sort | perturbatively selected configuration-interaction
wave functions for efficient geometry optimization in quantum monte
carlo |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6096455/ https://www.ncbi.nlm.nih.gov/pubmed/29953810 http://dx.doi.org/10.1021/acs.jctc.8b00393 |
work_keys_str_mv | AT dashmonika perturbativelyselectedconfigurationinteractionwavefunctionsforefficientgeometryoptimizationinquantummontecarlo AT moronisaverio perturbativelyselectedconfigurationinteractionwavefunctionsforefficientgeometryoptimizationinquantummontecarlo AT scemamaanthony perturbativelyselectedconfigurationinteractionwavefunctionsforefficientgeometryoptimizationinquantummontecarlo AT filippiclaudia perturbativelyselectedconfigurationinteractionwavefunctionsforefficientgeometryoptimizationinquantummontecarlo |