Physical Review Letters ( IF 8.385 ) Pub Date : 2021-02-22 , DOI: 10.1103/physrevlett.126.087401
Carlos M. Bustamante; Esteban D. Gadea; Andrew Horsfield; Tchavdar N. Todorov; Mariano C. González Lebrero; Damián A. Scherlis

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 ${\mathrm{C}}^{2+}$, ${\mathrm{B}}^{+}$, 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.

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