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Computation 2016, 4(1), 10; doi:10.3390/computation4010010

Localized Polycentric Orbital Basis Set for Quantum Monte Carlo Calculations Derived from the Decomposition of Kohn-Sham Optimized Orbitals

Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Giuseppe Moruzzi 13, Pisa 56124, Italy
These authors contributed equally to this work.
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Received: 10 December 2015 / Accepted: 28 January 2016 / Published: 6 February 2016
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Abstract

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–Jastrow 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. View Full-Text
Keywords: Kohn-Sham orbitals; quantum Monte Carlo; electronic structure of molecules Kohn-Sham orbitals; quantum Monte Carlo; electronic structure of molecules
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Amovilli, C.; Floris, F.M.; Grisafi, A. Localized Polycentric Orbital Basis Set for Quantum Monte Carlo Calculations Derived from the Decomposition of Kohn-Sham Optimized Orbitals. Computation 2016, 4, 10.

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