Manipulating nonadiabatic conical intersection dynamics by optical cavities

Optical cavities hold great promise to manipulate and control the photochemistry of molecules. We demonstrate how molecular photochemical processes can be manipulated by strong light-matter coupling. For a molecule with an inherent conical intersection, optical cavities can induce significant changes in the nonadiabatic dynamics by either splitting the pristine conical intersections into two novel polaritonic conical intersections or by creating light-induced avoided crossings in the polaritonic surfaces. This is demonstrated by exact real-time quantum dynamics simulations of a three-state two-mode model of pyrazine strongly coupled to a single cavity photon mode. We further explore the effects of external environments through dissipative polaritonic dynamics computed using the hierarchical equation of motion method. We find that cavity-controlled photochemistry can be immune to external environments. We demonstrate that the polariton-induced changes in the dynamics can be monitored by transient absorption spectroscopy.

References

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Zhedong Zhang, Prasoon Saurabh , Konstantin E. Dorfman ,Arunangshu Debnath, and Shaul Mukamel, "Monitoring polaritons dynamics in the LHCII photosynthetic antenna in a microcavity by two-photon coincidence counting", J.Chem. Phys, 148, 074302 (2018)