Published: Aug. 16, 2024
Experimental demonstrations of modified chemical structure and reactivity under strong light-matter coupling have spurred theoretical computational efforts to uncover underlying mechanisms. Ab initio cavity quantum electrodynamics (QED) combines chemistry with QED investigate these phenomena in detail. Unitary transformations ab Hamiltonians been used make them more computationally tractable. We analyze one such transformation, the coherent state using perturbation theory. Applying theory up third order for ground energies potential energy surfaces electronic coupling, we show that transformation yields better agreement exact energies. Additionally, apply second mode states bilinear elucidating how accelerates convergence photonic subspace towards complete basis limit renders molecular ion origin invariant. These findings contribute valuable insights into advantages context methods.
Language: Английский