Role of Cavity Losses on Nonadiabatic Couplings and Dynamics in Polaritonic Chemistry

Abstract

We present a non-Hermitian formulation of the polaritonic structure of azobenzene strongly coupled to a photonic mode that explicitly accounts for the fleeting nature of the photon-molecule interaction. This formalism reveals that the polaritonic non-adiabatic couplings that facilitate cis-trans isomerization can be dramatically modified by photonic dissipation. We perform Fewest-Switches Surface Hopping dynamics on the surfaces that derive from our non-Hermitian formalism and find that the polaritonic isomerization yields are strongly suppressed for moderate to large photon dissipation rates. These findings highlight the important role that the finitelifetime of photonic degrees of freedom play in polaritonic chemistry. File list (2) download file view on ChemRxiv Polaritonic_Chemistry_v2_main.pdf (1.99 MiB) download file view on ChemRxiv Polaritonic_Chemistry_v2_SI.pdf (479.09 KiB)

Non-Hermitian Cavity Quantum Electrodynamics - Configuration Interaction Singles Approach for Polaritonic Structure with ab initio Molecular Hamiltonians

“…We see with a pure real photon energy, the |LP and |UP surfaces experience a strong splitting in the region where the |X, 1 state (the ground-state plus a photon) crosses the |A, 0 state (the first excited-state without a photon). However, for the strongly dissipative photon, we see that both the model and CQED-CIS curves closely approximate the CIS curves for the lone molecules, which signals that this system is not in the strong-coupling regime because of the lossiness associated with the photon 25 .…”

“…In the above, b † and b are the bosonic raising/lowering operators for the photonic degrees of freedom, and ω = ω − i γ 2 is a complex frequency of the photon with the real part ω being related to the energy of the photon, and the imaginary part γ being related to the dissipation rate of the photonic degree of freedom 18,25,37 . The term µ represents the ground state molecular dipole expectation value which has cartesian components ξ ∈ {x, y, z}.…”

Non-Hermitian Cavity Quantum Electrodynamics - Configuration Interaction Singles Approach for Polaritonic Structure with ab initio Molecular Hamiltonians

“…We consider the real part of the photon energy to be 4.75 eV, and we consider the imaginary part to be either 0 eV or 0.22 eV as shown in the top and bottom panels of Figure 3, respectively. In addition to computing these polariton surfaces at the CQED-CIS/cc-pVDZ level, we also fit a 3-level model Pauli-Fierz Hamiltonian from ordinary CIS/cc-pVDZ potential energy surfaces: for the strongly dissipative photon, we see that both the model and CQED-CIS curves closely approximate the CIS curves for the lone molecules, which signals that this system is not in the strong-coupling regime because of the lossiness associated with the photon 25 .…”

“…In the above,b † andb are the bosonic raising/lowering operators for the photonic degrees of freedom, andω = ω − i γ 2 is a complex frequency of the photon with the real part ω being related to the energy of the photon, and the imaginary part γ being related to the dissipation rate of the photonic degree of freedom 18,25,37 . The term µ represents the ground state molecular dipole expectation value which has cartesian components ξ ∈ {x, y, z}.…”

Hyperbolic Shear Polaritons in Low-Symmetry Crystals

“…These observations naturally link HShPs in monoclinic crystals to the rich emerging area of non-Hermitian and topological photonics. While loss in orthogonal systems alone can already have interesting consequences for polariton propagation 46 , the off-diagonal shear dissipation highlighted here can provide new opportunities for non-Hermitian photonics and for manipulation of topological polaritons in low-symmetry materials. For instance, we envision asymmetric topological transitions experienced by HShPs, generalizing previous results in orthorhombic systems 2 by exploiting the unique non-Hermitian features emerging in low-symmetry materials.…”