Merging the Energy Decomposition Analysis with the Interacting Quantum Atoms Approach
dc.contributor.author
dc.date.accessioned
2023-10-27T06:05:01Z
dc.date.available
2023-10-27T06:05:01Z
dc.date.issued
2023-05-29
dc.identifier.issn
1549-9618
dc.identifier.uri
dc.description.abstract
Energy decomposition analysis (EDA) is a well-established approach to dissect the interaction energy into chemically sound components. Despite the inherent requirement of reference states has been a long-standing object of debate, the direct relation with the molecular orbital analysis helps in building up predictive models. The alternative molecular energy decomposition schemes that decompose the total energy into atomic and diatomic contributions, such as the interacting quantum atoms (IQA), has no external reference requirements and also the intra- and intermolecular interactions are treated on equal footing. However, a connection with heuristic chemical models are limited, bringing about a somewhat narrower predictive power. While efforts to reconcile the bonding picture obtained by both methodologies have been discussed in the past, a synergic combination of them has not been tackled yet. Herein, we present the use of IQA decomposition of the individual terms arising from the EDA in the context of intermolecular interactions, henceforth EDA–IQA. The method is applied to a molecular set covering a wide range of interaction types, including hydrogen bonding, charge–dipole, π–π and halogen interactions. We find that the electrostatic energy from EDA, entirely seen as intermolecular, leads to meaningful and non-negligible intra-fragment contributions upon IQA decomposition, originated from charge penetration. EDA–IQA also affords the decomposition of the Pauli repulsion term into intra- and inter-fragment contributions. The intra-fragment term is destabilizing, particularly for the moieties that are net acceptors of charge, while the inter-fragment Pauli term is actually stabilizing. In the case of the orbital interaction term, the sign and magnitude of the intra-fragment contribution at equilibrium geometries is largely driven by the amount of charge transfer, while the inter-fragment contribution is clearly stabilizing. EDA–IQA terms show a smooth behavior along the intermolecular dissociation path of selected systems. The new EDA–IQA methodology provides a richer energy decomposition scheme that aims at bridging the gap between the two main distinct real-space and Hilbert-space methodologies. Via this approach, the partitioning can be used directionally on all the EDA terms aiding in identifying the causal effects on geometries and/or reactivity
dc.description.sponsorship
M.G. Thanks the Fons Social Europeu and the Generalitat de Catalunya for the predoctoral fellowship (Grant 2018 FI_B 01120). P.S. and M.G. were supported by the Ministerio de Ciencia, Innovacion y Universidades (MCIU) Grant PGC2018-098212-B-C22. S.D and D.M.A. thanks the European Research Council (EU805113).
Open Access funding provided thanks to the CRUE-CSIC agreement with American Chemical Society (ACS)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
PGC2018-098212-B-C22
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Reproducció digital del document publicat a: https://doi.org/10.1021/acs.jctc.3c00143
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Journal of Chemical Theory and Computation, 2023, vol. 19, núm. 12, p. 3469-3485
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Articles publicats (D-Q)
dc.rights
Attribution 4.0 International
dc.rights.uri
dc.title
Merging the Energy Decomposition Analysis with the Interacting Quantum Atoms Approach
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.relation.projectID
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-098212-B-C22/ES/DESCOMPOSICION EN EL ESPACIO REAL DE PROPIEDADES OPTICAS NO LINEALES PARA EL DISEÑO RACIONAL DE MATERIALES OPTOELECTRONICOS/
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1549-9626