Polaritonic chemistry has ushered in new avenues for controlling molecular dynamics. However, two key questions remain: (i) Can classical light sources elicit the same effects as certain quantum light sources on molecular systems? (ii) Can semiclassical treatments of light–matter interactions capture nontrivial quantum effects observed in molecular dynamics? This work presents a quantum-classical approach addressing issues of realizing cavity chemistry effects without actual cavities. It also highlights the limitations of the standard semiclassical light–matter interaction. It is demonstrated that classical light sources can mimic quantum effects up to the second order of light–matter interaction provided that the mean-field contribution, the symmetrized two-time correlation function, and the linear response function are the same in both situations. Numerical simulations show that the quantum-classical method aligns more closely with exact quantum molecular-only dynamics for quantum light states such as Fock states, superpositions of Fock states, and vacuum squeezed states than does the conventional semiclassical approach.
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