TY - JOUR

T1 - Dissipative equation of motion for electromagnetic radiation in quantum dynamics

AU - Bustamante, Carlos

AU - Gadea, Esteban

AU - Horsfield, Andrew P.

AU - Todorov, Tchavdar

AU - Gonzalez Lebrero, Mariano

AU - Scherlis, Damian A.

PY - 2021/2/11

Y1 - 2021/2/11

N2 - 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 modelling, 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.

AB - 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 modelling, 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.

M3 - Article

JO - Physical Review Letters

JF - Physical Review Letters

SN - 0031-9007

ER -