Next Article in Journal
Applications of Computational Modelling and Simulation of Porous Medium in Tissue Engineering
Next Article in Special Issue
Influence of the Localization of Ge Atoms within the Si(001)(4 × 2) Surface Layer on Semicore One-Electron States
Previous Article in Journal
Computation of the Likelihood of Joint Site Frequency Spectra Using Orthogonal Polynomials
Previous Article in Special Issue
Optical Properties of Silicon-Rich Silicon Nitride (SixNyHz) from First Principles
Article

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
*
Author to whom correspondence should be addressed.
These authors contributed equally to this work.
Computation 2016, 4(1), 10; https://doi.org/10.3390/computation4010010
Received: 10 December 2015 / Accepted: 28 January 2016 / Published: 6 February 2016
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
Show Figures

Graphical abstract

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. https://doi.org/10.3390/computation4010010

AMA Style

Amovilli C, Floris FM, Grisafi A. Localized Polycentric Orbital Basis Set for Quantum Monte Carlo Calculations Derived from the Decomposition of Kohn-Sham Optimized Orbitals. Computation. 2016; 4(1):10. https://doi.org/10.3390/computation4010010

Chicago/Turabian Style

Amovilli, Claudio, Franca M. Floris, and Andrea Grisafi. 2016. "Localized Polycentric Orbital Basis Set for Quantum Monte Carlo Calculations Derived from the Decomposition of Kohn-Sham Optimized Orbitals" Computation 4, no. 1: 10. https://doi.org/10.3390/computation4010010

Find Other Styles
Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Article Access Map by Country/Region

1
Back to TopTop