Exciton-Plasmon States in Nanoscale Materials: Breakdown of the Tamm−Dancoff Approximation

Within the Tamm−Dancoff approximation, ab initio approaches describe excitons as packets of electron−hole pairs propagating only forward in time. However, we show that in nanoscale materials excitons and plasmons hybridize, creating exciton-plasmon states where the electron−hole pairs oscillate back and forth in time. Then, as exemplified by the trans-azobenzene molecule and the carbon nanotubes, the Tamm−Dancoff approximation yields errors larger than the accuracy claimed in ab initio calculations. Instead, we propose a general and efficient approach that avoids the Tamm−Dancoff approximation, correctly describes excitons, plasmons, and exciton-plasmon states, and provides a good agreement with experimental results.