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)

WPTherml is a Python package for the design of materials with tailored optical and thermal properties for the vast number of energy applications where control of absorption and emission of radiation, or conversion of heat to radiation or vice versa, is paramount. The optical properties are treated within classical electrodynamics via the Transfer Matrix Method which rigorously solves Maxwell's equations for layered isotropic media. A flexible multilayer class connects rigorous electrodynamics properties to figures of merit for a variety of thermal applications, and facilitates extensions to other applications for greater reuse potential. WPTherml can be accessed at https://github.com/FoleyLab/wptherml.

<p>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 the cis-trans isomerization can be dramatically modified by the inclusion of the photonic dissipation into the polaritonic Hamiltonian. We perform Fewest-Switches Surface Hopping dynamics on the surfaces that derive from our non-Hermitian formalism and find that the polaritonic isomerization rates are strongly suppressed for moderate to large photon dissipation rates. These findings highlight the important role that the nite lifetime of photonic degrees of freedom play in polaritonic chemistry.</p>

<p>WPTherml is a Python package for the design of materials with tailored optical and thermal properties for the vast number of energy applications where control of absorption and emission of radiation, or conversion of heat to radiation or vice versa, is paramount. The optical properties are treated within classical electrodynamics via the Transfer Matrix Method which rigorously solve Maxwell's equations for layered isotropic media. A flexible multilayer class connects rigorous electrodynamics properties to figures of merit for a variety of thermal applications, and facilitates extensions to other applications for greater reuse potential. WPTherml can be accessed at https://github.com/FoleyLab/wptherml. </p>

Multilayer nanostructures represent an important class of materials with tunable optical and thermal radiative properties that can be leveraged for a wide range of energy applications. We present a theoretical framework for optimizing the geometry of such structures that utilizes gradients of various objective functions that are enabled through analytic differentiation of the transfer-matrix equations. We demonstrate the usefulness of this method by applying it to the local optimization of many-degree-of-freedom structures for incandescent light sources, and the global optimization of few-degree-of-freedom structures that serve as solar cell coatings and optical cavities for enhancing the absorption of organic chromophores embedded in thin films.

<p>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 finite</p><p>lifetime of photonic degrees of freedom play in polaritonic chemistry.</p>

<div>Multilayer nanostructures represent an important class of materials with tunable optical and thermal radiative properties that can be leveraged for a wide range of energy applications. We present a theoretical framework for optimizing the geometry of such structures that utilizes gradients of various objective functions that are enabled through analytic differentiation of the transfer matrix equations. We demonstrate the usefulness of this method by applying it to the optimization of structures for incandescent light sources, and the global optimization of anti-reflective solar cell coatings.</div>

<p>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 the cis-trans isomerization can be dramatically modified by the inclusion of the photonic dissipation into the polaritonic Hamiltonian. We perform Fewest-Switches Surface Hopping dynamics on the surfaces that derive from our non-Hermitian formalism and find that the polaritonic isomerization rates are strongly suppressed for moderate to large photon dissipation rates. These findings highlight the important role that the nite lifetime of photonic degrees of freedom play in polaritonic chemistry.</p>