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The quantum photodynamics of a simple diatomic molecule with a permanentdipole immersed within an optical cavity containing a quantized radiation fieldis studied in detail. The chosen molecule under study, lithium fluoride (LiF),is characterized by the presence of an avoided crossing between the two lowest$^1\Sigma$ potential energy curves (covalent-ionic diabatic crossing). Withoutfield, after prompt excitation from the ground state $1\; ^1\Sigma$, theexcited nuclear wave packet moves back and forth in the upper $2\; ^1\Sigma$state, but in the proximity of the avoided crossing, the non-adiabatic couplingtransfers part of the nuclear wave packet to the lower $1\; ^1\Sigma$ state,which eventually leads to dissociation. The quantized field of a cavity alsoinduces an additional light crossing in the modified dressed potential energycurves with similar transfer properties. To understand the entangledphotonic-nuclear dynamics we solve the time dependent Schr\"odinger equation byusing the multiconfigurational time dependent Hartree method (MCTDH). Thesingle mode quantized field of the cavity is represented in the coordinatespace instead of in the Fock space, which allows us to deal with the field asan additional vibrational mode within the MCTDH procedure on equal footing. Weprepare the cavity with different quantum states of light, namely, Fock states,coherent states and squeezed coherent states. Our results reveal pure quantumlight effects on the molecular photodynamics and the dissociation yields ofLiF, which are quite different from the light-undressed case and that cannot bedescribed in general by a semiclassical approach using classicalelectromagnetic fields.

Entangled Photonic-Nuclear Molecular Dynamics of LiF in Quantum Optical Cavities