Pauli principle in polaritonic chemistry

Szidarovszky, Tamás (2023) Pauli principle in polaritonic chemistry. PHYSICAL REVIEW A. ISSN 2469-9926 (Submitted)

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Abstract

Consequences of enforcing permutational symmetry, as required by the Pauli principle (spinstatistical theorem), on the state space of molecular ensembles interacting with the quantized radiation mode of a cavity are discussed. The Pauli-allowed collective states are obtained by means of group theory, i.e., by projecting the state space onto the appropriate irreducible representations of the permutation group of the indistinguishable molecules. It is shown that with increasing number of molecules the ratio of Pauli-allowed collective states decreases very rapidly. Bosonic states are more abundant than fermionic states, and the brightness of Pauli-allowed state space (contribution from photon excited states) increases(decreases) with increasing fine structure in the energy levels of the material ground(excited) state manifold. Numerical results are shown for the realistic example of rovibrating H2O molecules interacting with an infrared (IR) cavity mode.

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