Variational reduced density matrix method in the doubly occupied configuration interaction space using three-particle N -representability conditions
Ground-state energies and two-particle reduced density matrices (2-RDMs) corresponding to N-particle systems are computed variationally within the doubly occupied configuration interaction (DOCI) space by constraining the 2-RDM to satisfy a complete set of three-particle N-representability condition...
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todo:paper_00219606_v149_n19_p_Alcoba2023-10-03T14:24:39Z Variational reduced density matrix method in the doubly occupied configuration interaction space using three-particle N -representability conditions Alcoba, D.R. Capuzzi, P. Rubio-García, A. Dukelsky, J. Massaccesi, G.E. Oña, O.B. Torre, A. Lain, L. Computation theory Matrix algebra Quantum chemistry Quantum theory Variational techniques Computational costs Configuration interactions Ground-state energies Positivity conditions Reduced-density matrix Repulsive interactions Semi-definite programming Variational calculation Ground state Ground-state energies and two-particle reduced density matrices (2-RDMs) corresponding to N-particle systems are computed variationally within the doubly occupied configuration interaction (DOCI) space by constraining the 2-RDM to satisfy a complete set of three-particle N-representability conditions known as three-positivity conditions. These conditions are derived and implemented in the variational calculation of the 2-RDM with standard semidefinite programming algorithms. Ground state energies and 2-RDMs are computed for N2, CO, CN-, and NO+ molecules at both equilibrium and nonequilibrium geometries as well as for pairing models at different repulsive interaction strengths. The results from the full three-positivity conditions are compared with those from the exact DOCI method and with approximated 2-RDM variational ones obtained within two-positivity and two-positivity plus a subset of three-positivity conditions, as recently reported [D. R. Alcoba et al., J. Chem. Phys. 148, 024105 (2018) and A. Rubio-García et al., J. Chem. Theory Comput. 14, 4183 (2018)]. The accuracy of these numerical determinations and their low computational cost demonstrate the usefulness of the three-particle variational constraints within the DOCI framework. © 2018 Author(s). JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00219606_v149_n19_p_Alcoba |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
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R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Computation theory Matrix algebra Quantum chemistry Quantum theory Variational techniques Computational costs Configuration interactions Ground-state energies Positivity conditions Reduced-density matrix Repulsive interactions Semi-definite programming Variational calculation Ground state |
| spellingShingle |
Computation theory Matrix algebra Quantum chemistry Quantum theory Variational techniques Computational costs Configuration interactions Ground-state energies Positivity conditions Reduced-density matrix Repulsive interactions Semi-definite programming Variational calculation Ground state Alcoba, D.R. Capuzzi, P. Rubio-García, A. Dukelsky, J. Massaccesi, G.E. Oña, O.B. Torre, A. Lain, L. Variational reduced density matrix method in the doubly occupied configuration interaction space using three-particle N -representability conditions |
| topic_facet |
Computation theory Matrix algebra Quantum chemistry Quantum theory Variational techniques Computational costs Configuration interactions Ground-state energies Positivity conditions Reduced-density matrix Repulsive interactions Semi-definite programming Variational calculation Ground state |
| description |
Ground-state energies and two-particle reduced density matrices (2-RDMs) corresponding to N-particle systems are computed variationally within the doubly occupied configuration interaction (DOCI) space by constraining the 2-RDM to satisfy a complete set of three-particle N-representability conditions known as three-positivity conditions. These conditions are derived and implemented in the variational calculation of the 2-RDM with standard semidefinite programming algorithms. Ground state energies and 2-RDMs are computed for N2, CO, CN-, and NO+ molecules at both equilibrium and nonequilibrium geometries as well as for pairing models at different repulsive interaction strengths. The results from the full three-positivity conditions are compared with those from the exact DOCI method and with approximated 2-RDM variational ones obtained within two-positivity and two-positivity plus a subset of three-positivity conditions, as recently reported [D. R. Alcoba et al., J. Chem. Phys. 148, 024105 (2018) and A. Rubio-García et al., J. Chem. Theory Comput. 14, 4183 (2018)]. The accuracy of these numerical determinations and their low computational cost demonstrate the usefulness of the three-particle variational constraints within the DOCI framework. © 2018 Author(s). |
| format |
JOUR |
| author |
Alcoba, D.R. Capuzzi, P. Rubio-García, A. Dukelsky, J. Massaccesi, G.E. Oña, O.B. Torre, A. Lain, L. |
| author_facet |
Alcoba, D.R. Capuzzi, P. Rubio-García, A. Dukelsky, J. Massaccesi, G.E. Oña, O.B. Torre, A. Lain, L. |
| author_sort |
Alcoba, D.R. |
| title |
Variational reduced density matrix method in the doubly occupied configuration interaction space using three-particle N -representability conditions |
| title_short |
Variational reduced density matrix method in the doubly occupied configuration interaction space using three-particle N -representability conditions |
| title_full |
Variational reduced density matrix method in the doubly occupied configuration interaction space using three-particle N -representability conditions |
| title_fullStr |
Variational reduced density matrix method in the doubly occupied configuration interaction space using three-particle N -representability conditions |
| title_full_unstemmed |
Variational reduced density matrix method in the doubly occupied configuration interaction space using three-particle N -representability conditions |
| title_sort |
variational reduced density matrix method in the doubly occupied configuration interaction space using three-particle n -representability conditions |
| url |
http://hdl.handle.net/20.500.12110/paper_00219606_v149_n19_p_Alcoba |
| work_keys_str_mv |
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| _version_ |
1807320773619089408 |