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 , , and Be, of 0.565, 0.831, and 1.97 ns, respectively, in accord with experimental values of , , 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.
- Received 7 August 2020
- Accepted 19 January 2021
- Corrected 19 March 2021
DOI:https://doi.org/10.1103/PhysRevLett.126.087401
© 2021 American Physical Society
Physics Subject Headings (PhySH)
Corrections
19 March 2021
Correction: The byline footnote for the third author contained an error and has been fixed.