Polynomial scaling approximations and dynamic correlation corrections to doubly occupied configuration interaction wave functions

A class of polynomial scaling methods that approximate Doubly Occupied Configuration Interaction (DOCI) wave functions and improve the description of dynamic correlation is introduced. The accuracy of the resulting wave functions is analysed by comparing energies and studying the overlap between the...

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Autores principales: Van Raemdonck, M., Alcoba, D.R., Poelmans, W., De Baerdemacker, S., Torre, A., Lain, L., Massaccesi, G.E., Van Neck, D., Bultinck, P.
Formato: JOUR
Materias:
Algorithms
Optimization
Quantum chemistry
Simulated annealing
Computationally efficient
Configuration interactions
Dynamic correlation
Energy-based algorithms
Full configuration interaction
Scaling method
Simulated annealing method
Single particle
Wave functions
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00219606_v143_n10_p_VanRaemdonck
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_00219606_v143_n10_p_VanRaemdonck
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spelling todo:paper_00219606_v143_n10_p_VanRaemdonck2023-10-03T14:24:34Z Polynomial scaling approximations and dynamic correlation corrections to doubly occupied configuration interaction wave functions Van Raemdonck, M. Alcoba, D.R. Poelmans, W. De Baerdemacker, S. Torre, A. Lain, L. Massaccesi, G.E. Van Neck, D. Bultinck, P. Algorithms Optimization Quantum chemistry Simulated annealing Computationally efficient Configuration interactions Dynamic correlation Energy-based algorithms Full configuration interaction Scaling method Simulated annealing method Single particle Wave functions A class of polynomial scaling methods that approximate Doubly Occupied Configuration Interaction (DOCI) wave functions and improve the description of dynamic correlation is introduced. The accuracy of the resulting wave functions is analysed by comparing energies and studying the overlap between the newly developed methods and full configuration interaction wave functions, showing that a low energy does not necessarily entail a good approximation of the exact wave function. Due to the dependence of DOCI wave functions on the single-particle basis chosen, several orbital optimisation algorithms are introduced. An energy-based algorithm using the simulated annealing method is used as a benchmark. As a computationally more affordable alternative, a seniority number minimising algorithm is developed and compared to the energy based one revealing that the seniority minimising orbital set performs well. Given a well-chosen orbital basis, it is shown that the newly developed DOCI based wave functions are especially suitable for the computationally efficient description of static correlation and to lesser extent dynamic correlation. © 2015 AIP Publishing LLC. Fil:Massaccesi, G.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00219606_v143_n10_p_VanRaemdonck
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Algorithms
Optimization
Quantum chemistry
Simulated annealing
Computationally efficient
Configuration interactions
Dynamic correlation
Energy-based algorithms
Full configuration interaction
Scaling method
Simulated annealing method
Single particle
Wave functions
spellingShingle Algorithms
Optimization
Quantum chemistry
Simulated annealing
Computationally efficient
Configuration interactions
Dynamic correlation
Energy-based algorithms
Full configuration interaction
Scaling method
Simulated annealing method
Single particle
Wave functions
Van Raemdonck, M.
Alcoba, D.R.
Poelmans, W.
De Baerdemacker, S.
Torre, A.
Lain, L.
Massaccesi, G.E.
Van Neck, D.
Bultinck, P.
Polynomial scaling approximations and dynamic correlation corrections to doubly occupied configuration interaction wave functions
topic_facet Algorithms
Optimization
Quantum chemistry
Simulated annealing
Computationally efficient
Configuration interactions
Dynamic correlation
Energy-based algorithms
Full configuration interaction
Scaling method
Simulated annealing method
Single particle
Wave functions
description A class of polynomial scaling methods that approximate Doubly Occupied Configuration Interaction (DOCI) wave functions and improve the description of dynamic correlation is introduced. The accuracy of the resulting wave functions is analysed by comparing energies and studying the overlap between the newly developed methods and full configuration interaction wave functions, showing that a low energy does not necessarily entail a good approximation of the exact wave function. Due to the dependence of DOCI wave functions on the single-particle basis chosen, several orbital optimisation algorithms are introduced. An energy-based algorithm using the simulated annealing method is used as a benchmark. As a computationally more affordable alternative, a seniority number minimising algorithm is developed and compared to the energy based one revealing that the seniority minimising orbital set performs well. Given a well-chosen orbital basis, it is shown that the newly developed DOCI based wave functions are especially suitable for the computationally efficient description of static correlation and to lesser extent dynamic correlation. © 2015 AIP Publishing LLC.
format JOUR
author Van Raemdonck, M.
Alcoba, D.R.
Poelmans, W.
De Baerdemacker, S.
Torre, A.
Lain, L.
Massaccesi, G.E.
Van Neck, D.
Bultinck, P.
author_facet Van Raemdonck, M.
Alcoba, D.R.
Poelmans, W.
De Baerdemacker, S.
Torre, A.
Lain, L.
Massaccesi, G.E.
Van Neck, D.
Bultinck, P.
author_sort Van Raemdonck, M.
title Polynomial scaling approximations and dynamic correlation corrections to doubly occupied configuration interaction wave functions
title_short Polynomial scaling approximations and dynamic correlation corrections to doubly occupied configuration interaction wave functions
title_full Polynomial scaling approximations and dynamic correlation corrections to doubly occupied configuration interaction wave functions
title_fullStr Polynomial scaling approximations and dynamic correlation corrections to doubly occupied configuration interaction wave functions
title_full_unstemmed Polynomial scaling approximations and dynamic correlation corrections to doubly occupied configuration interaction wave functions
title_sort polynomial scaling approximations and dynamic correlation corrections to doubly occupied configuration interaction wave functions
url http://hdl.handle.net/20.500.12110/paper_00219606_v143_n10_p_VanRaemdonck
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