Mostrar el registro sencillo del ítem
dc.contributor.author
Bustamante, Carlos Mauricio
dc.contributor.author
Gadea, Esteban David
dc.contributor.author
Todorov, Tchavdar N.
dc.contributor.author
Horsfield, Andrew
dc.contributor.author
Stella, Lorenzo
dc.contributor.author
Scherlis Perel, Damian Ariel
dc.date.available
2024-02-26T14:35:47Z
dc.date.issued
2023-04
dc.identifier.citation
Bustamante, Carlos Mauricio; Gadea, Esteban David; Todorov, Tchavdar N.; Horsfield, Andrew; Stella, Lorenzo; et al.; Fluorescence in quantum dynamics: Accurate spectra require post-mean-field approaches; American Institute of Physics; Journal of Chemical Physics; 158; 14; 4-2023; 1-12
dc.identifier.issn
0021-9606
dc.identifier.uri
http://hdl.handle.net/11336/228419
dc.description.abstract
Real time modeling of fluorescence with vibronic resolution entails the representation of the light–matter interaction coupled to a quantummechanical description of the phonons and is therefore a challenging problem. In this work, taking advantage of the difference in timescales characterizing internal conversion and radiative relaxation—which allows us to decouple these two phenomena by sequentially modeling one after the other—we simulate the electron dynamics of fluorescence through a master equation derived from the Redfield formalism. Moreover, we explore the use of a recent semiclassical dissipative equation of motion [C. M. Bustamante et al., Phys. Rev. Lett. 126, 087401 (2021)], termed coherent electron electric-field dynamics (CEED), to describe the radiative stage. By comparing the results with those from the full quantum-electrodynamics treatment, we find that the semiclassical model does not reproduce the right amplitudes in the emission spectra when the radiative process involves the de-excitation to a manifold of closely lying states. We argue that this flaw is inherent to any mean-field approach and is the case with CEED. This effect is critical for the study of light–matter interaction, and this work is, to our knowledge, the first one to report this problem. We note that CEED reproduces the correct frequencies in agreement with quantum electrodynamics. This is a major asset of the semiclassical model, since the emission peak positions will be predicted correctly without any prior assumption about the nature of the molecular Hamiltonian. This is not so for the quantum electrodynamics approach, where access to the spectral information relies on knowledge of the Hamiltonian eigenvalues.
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
FLUORESCENCE
dc.subject
QUANTUM DYNAMICS
dc.subject
SEMICLASSICAL
dc.subject
RADIATIVE EMISSION
dc.subject.classification
Física Atómica, Molecular y Química
dc.subject.classification
Ciencias Físicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
Fluorescence in quantum dynamics: Accurate spectra require post-mean-field approaches
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2024-02-26T11:10:56Z
dc.journal.volume
158
dc.journal.number
14
dc.journal.pagination
1-12
dc.journal.pais
Estados Unidos
dc.description.fil
Fil: Bustamante, Carlos Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
dc.description.fil
Fil: Gadea, Esteban David. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
dc.description.fil
Fil: Todorov, Tchavdar N.. The Queens University of Belfast; Irlanda
dc.description.fil
Fil: Horsfield, Andrew. Imperial College London; Reino Unido
dc.description.fil
Fil: Stella, Lorenzo. The Queens University of Belfast; Irlanda
dc.description.fil
Fil: Scherlis Perel, Damian Ariel. Universidad de Buenos Aires; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
dc.journal.title
Journal of Chemical Physics
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1063/5.0142094
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.aip.org/aip/jcp/article-abstract/158/14/144104/2877769/Fluorescence-in-quantum-dynamics-Accurate-spectra?redirectedFrom=fulltext
Archivos asociados