Dissipative equation of motion for electromagnetic radiation in quantum dynamics
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Accepted version
Author(s)
Type
Journal Article
Abstract
The dynamical description of the radiative decay of an electronically excited state in realistic many-particle systems is an unresolved challenge. In the present investigation electromagnetic radiation of the charge density is approximated as the power dissipated by a classical dipole, to cast the emission in closed form as a unitary single-electron theory. This results in a formalism of unprecedented efficiency, critical for ab initio modeling, which exhibits at the same time remarkable properties: it quantitatively predicts decay rates, natural broadening, and absorption intensities. Exquisitely accurate excitation lifetimes are obtained from time-dependent DFT simulations for C2+, B+, and Be, of 0.565, 0.831, and 1.97 ns, respectively, in accord with experimental values of 0.57±0.02, 0.86±0.07, and 1.77–2.5 ns. Hence, the present development expands the frontiers of quantum dynamics, bringing within reach first-principles simulations of a wealth of photophysical phenomena, from fluorescence to time-resolved spectroscopies.
Date Issued
2021-02-26
Date Acceptance
2021-01-20
Citation
Physical Review Letters, 2021, 126 (8)
ISSN
0031-9007
Publisher
American Physical Society
Journal / Book Title
Physical Review Letters
Volume
126
Issue
8
Copyright Statement
© 2021 American Physical Society.
Sponsor
Commission of the European Communities
Grant Number
823897
Subjects
Science & Technology
Physical Sciences
Physics, Multidisciplinary
Physics
General Physics
01 Mathematical Sciences
02 Physical Sciences
09 Engineering
Publication Status
Published
Article Number
ARTN 087401
Date Publish Online
2021-02-22