Polaritonic Chemistry by Javier Galego Pascual

Author:Javier Galego Pascual
Language: eng
Format: epub
ISBN: 9783030486983
Publisher: Springer International Publishing

We first address the applicability of the BOA, which breaks down when two PoPES are close in energy, for the case of two molecules. Within the single-excitation subspace (which determines the linear properties of the system, such as absorption), there are now a range of (avoided) crossings. They occur when (i) all three surfaces approach each other , (ii) the photonically excited PES is close to only one of the electronically excited PES, or , or (iii) only the two electronically excited states cross, . Case (i) corresponds to the TC model at zero detuning, giving the two polaritonic PES at energy shifts of , and an additional dark state that is unshifted from the bare-molecule case. The BOA in this region is thus valid for similar conditions as in the single-molecule case, although the PES separation is reduced by half due to the additional dark-state surface. Case (ii) corresponds exactly to the single-molecule case, with the second molecule acting as a “spectator” that only induces additional energy shifts. The BOA should thus again be valid for similar conditions as with a single-molecule, albeit with the coupling reduced by for a fixed total Rabi splitting. Finally, case (iii) presents the biggest challenge, as the two electronically excited PES, and , are not directly coupled, but only split indirectly through coupling to the photonically excited surface . The splitting between the two surfaces is thus small for large detuning, . This is clearly observed in Fig. 3.7b along the line , where the dark state PES almost touches the upper PoPES for small Rs and the lower PoPES for large Rs.

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