In this work, we formulate the equations of motion corresponding to the Hermitian operator method in the framework of the doubly occupied configuration interaction space. The resulting algorithms turn out to be considerably simpler than the equations provided by that method in more conventional spaces, enabling the determination of excitation energies in N-electron systems under an affordable polynomial computational cost. The implementation of this technique only requires to know the elements of low-order reduced density matrices of an N-electron reference state, which can be obtained from any approximate method. We contrast our procedure against the reduced Bardeen–Cooper–Schrieffer and Richardson–Gaudin–Kitaev integrable models, pointing out the reliability of our proposal.
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28 September 2023
Research Article|
September 25 2023
Determination of electronic excitation energies within the doubly occupied configuration interaction space by means of the Hermitian operator method Available to Purchase
Adán Garros
;
Adán Garros
(Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Software, Validation, Visualization, Writing – original draft, Writing – review & editing)
1
Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Física, Ciudad Universitaria
, 1428 Buenos Aires, Argentina
2
CONICET–Universidad de Buenos Aires, Instituto de Física de Buenos Aires (IFIBA), Ciudad Universitaria
, 1428 Buenos Aires, Argentina
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Diego R. Alcoba
;
Diego R. Alcoba
(Conceptualization, Funding acquisition, Methodology, Software, Validation, Writing – review & editing)
1
Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Física, Ciudad Universitaria
, 1428 Buenos Aires, Argentina
2
CONICET–Universidad de Buenos Aires, Instituto de Física de Buenos Aires (IFIBA), Ciudad Universitaria
, 1428 Buenos Aires, Argentina
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Pablo Capuzzi
;
Pablo Capuzzi
a)
(Conceptualization, Funding acquisition, Methodology, Software, Validation, Writing – review & editing)
1
Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Física, Ciudad Universitaria
, 1428 Buenos Aires, Argentina
2
CONICET–Universidad de Buenos Aires, Instituto de Física de Buenos Aires (IFIBA), Ciudad Universitaria
, 1428 Buenos Aires, Argentina
a)Author to whom correspondence should be addressed: [email protected]
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Luis Lain
;
Luis Lain
(Validation, Writing – original draft, Writing – review & editing)
3
Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco
, Apdo. 644, E-48080 Bilbao, Spain
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Alicia Torre
;
Alicia Torre
(Validation, Writing – original draft, Writing – review & editing)
3
Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco
, Apdo. 644, E-48080 Bilbao, Spain
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Ofelia B. Oña
;
Ofelia B. Oña
(Methodology, Software, Validation, Writing – review & editing)
4
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Universidad Nacional de La Plata, Consejo Nacional de Investigaciones Científicas y Técnicas
, Diag. 113 y 64 (S/N), Sucursal 4, CC 16, 1900 La Plata, Argentina
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Jorge Dukelsky
Jorge Dukelsky
(Conceptualization, Methodology, Writing – review & editing)
5
Instituto de Estructura de la Materia, CSIC
, Serrano 123, E-28006 Madrid, Spain
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Adán Garros
1,2
Diego R. Alcoba
1,2
Pablo Capuzzi
1,2,a)
Luis Lain
3
Alicia Torre
3
Ofelia B. Oña
4
Jorge Dukelsky
5
1
Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Física, Ciudad Universitaria
, 1428 Buenos Aires, Argentina
2
CONICET–Universidad de Buenos Aires, Instituto de Física de Buenos Aires (IFIBA), Ciudad Universitaria
, 1428 Buenos Aires, Argentina
3
Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco
, Apdo. 644, E-48080 Bilbao, Spain
4
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Universidad Nacional de La Plata, Consejo Nacional de Investigaciones Científicas y Técnicas
, Diag. 113 y 64 (S/N), Sucursal 4, CC 16, 1900 La Plata, Argentina
5
Instituto de Estructura de la Materia, CSIC
, Serrano 123, E-28006 Madrid, Spain
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 159, 124107 (2023)
Article history
Received:
July 19 2023
Accepted:
September 06 2023
Citation
Adán Garros, Diego R. Alcoba, Pablo Capuzzi, Luis Lain, Alicia Torre, Ofelia B. Oña, Jorge Dukelsky; Determination of electronic excitation energies within the doubly occupied configuration interaction space by means of the Hermitian operator method. J. Chem. Phys. 28 September 2023; 159 (12): 124107. https://doi.org/10.1063/5.0168585
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