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      Perturbatively Selected Configuration-Interaction Wave Functions for Efficient Geometry Optimization in Quantum Monte Carlo

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          Abstract

          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.

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          Most cited references 41

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          Iterative perturbation calculations of ground and excited state energies from multiconfigurational zeroth‐order wavefunctions

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            Configuration Interaction in Orbital Theories

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              The Stark Effect from the Point of View of Schroedinger's Quantum Theory

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                Author and article information

                Journal
                J Chem Theory Comput
                J Chem Theory Comput
                ct
                jctcce
                Journal of Chemical Theory and Computation
                American Chemical Society
                1549-9618
                1549-9626
                28 June 2018
                14 August 2018
                : 14
                : 8
                : 4176-4182
                Affiliations
                []MESA+ Institute for Nanotechnology, University of Twente , P.O. Box 217, 7500 AE Enschede, The Netherlands
                []CNR-IOM DEMOCRITOS, Istituto Officina dei Materiali, and SISSA Scuola Internazionale Superiore di Studi Avanzati , Via Bonomea 265, I-34136 Trieste, Italy
                [§ ]Laboratoire de Chimie et Physique Quantiques, Université de Toulouse , CNRS, UPS, 118 Route de Narbonne, 31077 Toulouse, France
                Author notes
                Article
                10.1021/acs.jctc.8b00393
                6096455
                29953810
                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, which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.

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                Custom metadata
                ct8b00393
                ct-2018-003939

                Computational chemistry & Modeling

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