Ultrafast Nonradiative Decay of a Dipolar Plasmon-like State in Naphthalene

Motivated by the uncertainty in our understanding of ultrafast plasmon decay mechanisms, we examine the effect of nuclear vibrations on the dynamical behavior of the strong plasmon-like dipole response of naphthalene, known as the β peak. The real-time time-dependent density functional (RT-TDDFT) method coupled with Ehrenfest molecular dynamics is used to describe the interconnected nuclear and electronic motion. Several vibrational modes promote drastic plasmon decay in naphthalene. The most astonishing finding of this study is that activation of one particular vibrational mode (corresponding to the B₁ representation in D₂ point group symmetry) leads to a continuous drop of the dipole response corresponding to the β peak into a totally symmetric, dark, quadrupolar electronic state. A second B₁ mode provokes the sharp plasmon-like peak to split due to the breaking of structural symmetry. Nonadiabatic coupling between a B₂ vibrational mode and the β peak (a B₁ electronic state) gives rise to a B₃ vibronic state, which can be identified as one of the p-band peaks that reside close in energy to the β peak energy. Overall, strong nonadiabatic coupling initiates plasmon decay into nearby electronic states in acenes, most importantly into dark states. These findings expand our knowledge about possible plasmon decay processes and pave the way for achieving high optical performance in acene-based materials such as graphene.