Author, as appears in the article.: Sanchez-Mansilla, A.; Sousa, C.; Kathir, R. K.; Broer, R.; Straatsma, T. P.; de Graaf, C.;
Department: Química Física i Inorgànica
URV's Author/s: De Graaf, Cornelis / Sánchez Mansilla, Aitor María
Keywords: Spin transitions Open-shell Implementation Hole states Hamiltonians Excitations Energy differences Broken orbital-symmetry Binuclear complexes 2nd-order perturbation-theory
Abstract: Two different approaches have been implemented to include the effect of dynamic electron correlation in the Non-Orthogonal Configuration Interaction for Fragments (NOCI-F) method. The first is based on shifting the diagonal matrix elements of the NOCI matrix, while the second incorporates the dynamic correlation explicitly in the fragment wave functions used to construct the many-electron basis functions of the NOCI. The two approaches are illustrated for the calculation of the electronic coupling relevant in singlet fission and the coupling of spin moments in organic radicals. Comparison of the calculated diabatic couplings, the NOCI energies and wave functions shows that dynamic electron correlation is not only efficiently but also effectively incorporated by the shifting approach and can largely affect the coupling between electronic states. Also, it brings the NOCI coupling of the spin moments in close agreement with benchmark calculations.
Thematic Areas: Química Physics, atomic, molecular & chemical Physics and astronomy (miscellaneous) Physics and astronomy (all) Physical and theoretical chemistry Odontología Medicina ii Medicina i Materiais Matemática / probabilidade e estatística Interdisciplinar Geociências General physics and astronomy General medicine Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Ciência de alimentos Ciência da computação Chemistry, physical Biotecnología Biodiversidade Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: coen.degraaf@urv.cat aitor.sanchezm@estudiants.urv.cat
Author identifier: 0000-0001-8114-6658
Record's date: 2024-09-07
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2022/cp/d2cp00772j
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Physical Chemistry Chemical Physics. 24 (19): 11931-11944
APA: Sanchez-Mansilla, A.; Sousa, C.; Kathir, R. K.; Broer, R.; Straatsma, T. P.; de Graaf, C.; (2022). On the role of dynamic electron correlation in non-orthogonal configuration interaction with fragments. Physical Chemistry Chemical Physics, 24(19), 11931-11944. DOI: 10.1039/d2cp00772j
Article's DOI: 10.1039/d2cp00772j
Entity: Universitat Rovira i Virgili
Journal publication year: 2022
Publication Type: Journal Publications
Repositori URV