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dc.contributor.author
Foglia, Nicolás Oscar
dc.contributor.author
Maganas, Dimitrios
dc.contributor.author
Neese, Frank
dc.date.available
2023-05-16T13:08:07Z
dc.date.issued
2022-08
dc.identifier.citation
Foglia, Nicolás Oscar; Maganas, Dimitrios; Neese, Frank; Going beyond the electric-dipole approximation in the calculation of absorption and (magnetic) circular dichroism spectra including scalar relativistic and spin-orbit coupling effects; American Institute of Physics; Journal of Chemical Physics; 157; 8; 8-2022; 1-17
dc.identifier.issn
0021-9606
dc.identifier.uri
http://hdl.handle.net/11336/197658
dc.description.abstract
In this work, a time-dependent density functional theory (TD-DFT) scheme for computing optical spectroscopic properties in the framework of linearly and circularly polarized light is presented. The scheme is based on a previously formulated theory for predicting optical absorption and magnetic circular dichroism (MCD) spectra. The scheme operates in the framework of the full semi-classical field-matter interaction operator, thus generating a powerful and general computational scheme capable of computing the absorption, circular dichroism (CD), and MCD spectra. In addition, our implementation includes the treatment of relativistic effects in the framework of quasidegenerate perturbation theory, which accounts for scalar relativistic effects (in the self-consistent field step) and spin-orbit coupling (in the TD-DFT step), as well as external magnetic field perturbations. Hence, this formalism is also able to probe spin-forbidden transitions. The random orientations of molecules are taken into account by a semi-numerical approach involving a Lebedev numerical quadrature alongside analytical integration. It is demonstrated that the numerical quadrature requires as few as 14 points for satisfactory converged results, thus leading to a highly efficient scheme, while the calculation of the exact transition moments creates no computational bottlenecks. It is demonstrated that at zero magnetic field, the CD spectrum is recovered, while the sum of left and right circularly polarized light contributions provides the linear absorption spectrum. The virtues of this efficient and general protocol are demonstrated on a selected set of organic molecules where the various contributions to the spectral intensities have been analyzed in detail.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Institute of Physics
dc.rights
info:eu-repo/semantics/restrictedAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
TD-DFT
dc.subject
MCD
dc.subject.classification
Físico-Química, Ciencia de los Polímeros, Electroquímica
dc.subject.classification
Ciencias Químicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
Going beyond the electric-dipole approximation in the calculation of absorption and (magnetic) circular dichroism spectra including scalar relativistic and spin-orbit coupling effects
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2023-05-16T11:24:33Z
dc.journal.volume
157
dc.journal.number
8
dc.journal.pagination
1-17
dc.journal.pais
Estados Unidos
dc.description.fil
Fil: Foglia, Nicolás Oscar. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
dc.description.fil
Fil: Maganas, Dimitrios. Max-Planck-Institut für Kohlenforschung; Alemania
dc.description.fil
Fil: Neese, Frank. Max-Planck-Institut für Kohlenforschung; Alemania
dc.journal.title
Journal of Chemical Physics
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1063/5.0094709
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