{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T04:17:55Z","timestamp":1760242675482,"version":"build-2065373602"},"reference-count":43,"publisher":"MDPI AG","issue":"1","license":[{"start":{"date-parts":[[2016,2,6]],"date-time":"2016-02-06T00:00:00Z","timestamp":1454716800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Computation"],"abstract":"<jats:p>In this work, we present a simple decomposition scheme of the Kohn-Sham optimized orbitals which is able to provide a reduced basis set, made of localized polycentric orbitals, specifically designed for Quantum Monte Carlo. The decomposition follows a standard Density functional theory (DFT) calculation and is based on atomic connectivity and shell structure. The new orbitals are used to construct a compact correlated wave function of the Slater\u2013Jastrow form which is optimized at the Variational Monte Carlo level and then used as the trial wave function for a final Diffusion Monte Carlo accurate energy calculation. We are able, in this way, to capture the basic information on the real system brought by the Kohn-Sham orbitals and use it for the calculation of the ground state energy within a strictly variational method. Here, we show test calculations performed on some small selected systems to assess the validity of the proposed approach in a molecular fragmentation, in the calculation of a barrier height of a chemical reaction and in the determination of intermolecular potentials. The final Diffusion Monte Carlo energies are in very good agreement with the best literature data within chemical accuracy.<\/jats:p>","DOI":"10.3390\/computation4010010","type":"journal-article","created":{"date-parts":[[2016,2,9]],"date-time":"2016-02-09T13:45:23Z","timestamp":1455025523000},"page":"10","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Localized Polycentric Orbital Basis Set for Quantum Monte Carlo Calculations Derived from the Decomposition of Kohn-Sham Optimized Orbitals"],"prefix":"10.3390","volume":"4","author":[{"given":"Claudio","family":"Amovilli","sequence":"first","affiliation":[{"name":"Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Giuseppe Moruzzi 13, Pisa 56124, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Franca","family":"Floris","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Giuseppe Moruzzi 13, Pisa 56124, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Andrea","family":"Grisafi","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Giuseppe Moruzzi 13, Pisa 56124, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2016,2,6]]},"reference":[{"key":"ref_1","first-page":"602","article-title":"Un metodo statistico per la determinazione di alcune propriet\u00e0 dell\u2019atomo","volume":"6","author":"Fermi","year":"1927","journal-title":"Rend. 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