Partitioning of interaction-induced nonlinear optical properties of molecular complexes. II. Halogen-bonded systems
dc.contributor.author
dc.date.accessioned
2020-04-03T08:28:45Z
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2020-04-03T08:28:45Z
dc.date.issued
2020-02-21
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1463-9076
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dc.description.abstract
Following our study on hydrogen-bonded (HB) complexes [Phys. Chem. Chem. Phys., 2018, 20, 19841], the physical nature of interaction-induced (non)linear optical properties of another important class of molecular complexes, namely halogen-bonded (XB) systems, was analyzed in this study. The excess electronic and nuclear relaxation (hyper)polarizabilities of nine representative XB complexes covering a wide range of halogen-bond strengths were computed. The partitioning of the excess properties into individual interaction-energy components (electrostatic, exchange, induction, dispersion) was performed by using the variational-perturbational energy decomposition scheme at the MP2/aug-cc-pVTZ level of theory and further supported by calculations with the SCS-MP2 method. In the case of the electronic interaction-induced properties, the physical composition of Δαel and Δγel was found to be very similar for the two types of bonding, despite the different nature of the binding. For Δβel, the XB complexes exhibit a more systematic interplay of interaction-energy contributions compared to the HB systems studied in the previous work. Our analysis revealed that the patterns of interaction-energy contributions to the interaction-induced nuclear-relaxation contributions to the linear polarizability and the first hyperpolarizability are very similar. For both properties the exchange repulsion term is canceled out by the electrostatic and delocalization terms. The physical composition of these contributions is analogous to those observed for the HB complexes
dc.description.sponsorship
J. M. L. is grateful for financial support from the Spanish MICIN PGC2018-098212-B-C22 and the Catalan DIUE 2017SGR39
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application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry (RSC)
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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/
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Versió postprint del document publicat a: https://doi.org/10.1039/C9CP06620A
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© Physical Chemistry Chemical Physics, 2020, vol. 22, núm. 7, p. 4225-4234
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Articles publicats (D-Q)
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Tots els drets reservats
dc.subject
dc.title
Partitioning of interaction-induced nonlinear optical properties of molecular complexes. II. Halogen-bonded systems
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2021-02-21
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
031265
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
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dc.identifier.eissn
1463-9084