Periodic Reporting for period 4 - CONICALM (Chemistry in Optical Nano Cavities: Designing Photonic Reagents and Light-Matter Materials)
Période du rapport: 2024-08-01 au 2025-07-31
Gaining detailed control over chemical reactions has always been a chemists dream. Quantum coherent control has been pursuing this dream by using specially tailored light fields to control chemical reactions on an atomistic level. With the advancement of cavity quantum electrodynamics and its recent application to molecules, using the quantum properties of light to control photochemistry has come into reach.
Recent, groundbreaking experiments have show that one can utilize the vacuum field of an optical nano-resonator to significantly modify the potential energy landscape and thus its photochemistry. The underlying effect is the formation of so-called "dressed states", which are created when the quantized radiation field mode couples to a molecular electronic transition. In the resulting coupled light-matter system, the molecular and the photonic degrees of freedom are heavily mixed. While this effect is well understood for atomic samples, it is not yet fully understood for molecules. The introduction of the nuclear degrees of freedom requires new theoretical frameworks. This effect can be used to modify reaction pathways of chemical and photochemical reactions. This opens a wide range of possibilities to engineer novel types of light driven catalysts.
The major objectives of this proposal are to advance the theoretical understanding of the underlying mechanisms, to build a suitable tool chest for numerical simulations, to use the insight and tools to propose new photochemical applications, and to close the gap between theory and experiment. We will theoretically investigate possibilities to optimize organic solar cells, and the photo catalytic schemes for environmentally relevant molecules.
Recent, groundbreaking experiments have show that one can utilize the vacuum field of an optical nano-resonator to significantly modify the potential energy landscape and thus its photochemistry. The underlying effect is the formation of so-called "dressed states", which are created when the quantized radiation field mode couples to a molecular electronic transition. In the resulting coupled light-matter system, the molecular and the photonic degrees of freedom are heavily mixed. While this effect is well understood for atomic samples, it is not yet fully understood for molecules. The introduction of the nuclear degrees of freedom requires new theoretical frameworks. This effect can be used to modify reaction pathways of chemical and photochemical reactions. This opens a wide range of possibilities to engineer novel types of light driven catalysts.
The major objectives of this proposal are to advance the theoretical understanding of the underlying mechanisms, to build a suitable tool chest for numerical simulations, to use the insight and tools to propose new photochemical applications, and to close the gap between theory and experiment. We will theoretically investigate possibilities to optimize organic solar cells, and the photo catalytic schemes for environmentally relevant molecules.
We have performed a bottom-up approach and have systematically investigated various effects of molecular strong light-matter coupling.
We have started by working on exploring collective effects, which are of fundamental importance in experiments but not yet very well understood.
This includes revisiting basic quantum optics models, such as the Tavis-Cummings model, and integrating electronic structure methods
quantized field modes.
We have extensively studied the influence of dissipative effects, such as the influence of poor mirrors with a high leakage.
We could demonstrate for the single-molecule model that leaky mirrors, which result in short photon lifetimes, play a crucial role in the reaction mechanism by using a high-level numerical method.
We also have studied various molecular systems and their photochemical properties under strong coupling.
These molecular systems include pyrrole, dioxetane, naphthalene, and BODIPY. Our studies could show that
in the single-molecule case, nonradiative dynamics could be modified by coupling electronic molecular transitions to
a quantized field mode. Depending on coupling strength and the resonance frequency, the excited states could either
be stabilized, or decay could be enhanced.
Molecular systems such as BODIPY are used in organic solar cell assembly and thus are interesting targets for
modification by means of a cavity.
We have developed and utilized electronic structure methods based on the cavity Born-Oppenheimer approximations.
These methods have allowed us to gain a more in-depth understanding of the interplay between tightly confined light fields and
the electronic structure of molecules. These effects are important for the understanding of collective interactions that
mediated by the quantized modes of the cavity.
We have started by working on exploring collective effects, which are of fundamental importance in experiments but not yet very well understood.
This includes revisiting basic quantum optics models, such as the Tavis-Cummings model, and integrating electronic structure methods
quantized field modes.
We have extensively studied the influence of dissipative effects, such as the influence of poor mirrors with a high leakage.
We could demonstrate for the single-molecule model that leaky mirrors, which result in short photon lifetimes, play a crucial role in the reaction mechanism by using a high-level numerical method.
We also have studied various molecular systems and their photochemical properties under strong coupling.
These molecular systems include pyrrole, dioxetane, naphthalene, and BODIPY. Our studies could show that
in the single-molecule case, nonradiative dynamics could be modified by coupling electronic molecular transitions to
a quantized field mode. Depending on coupling strength and the resonance frequency, the excited states could either
be stabilized, or decay could be enhanced.
Molecular systems such as BODIPY are used in organic solar cell assembly and thus are interesting targets for
modification by means of a cavity.
We have developed and utilized electronic structure methods based on the cavity Born-Oppenheimer approximations.
These methods have allowed us to gain a more in-depth understanding of the interplay between tightly confined light fields and
the electronic structure of molecules. These effects are important for the understanding of collective interactions that
mediated by the quantized modes of the cavity.
The theory developed within this project has extended the field of polaritonic chemistry beyond the state of the art.
We have developed a microscopic understanding of a broad variety of effects and how these effects do affect photochemical
reactions. We also have investigated various molecular species and estimated their controllability regarding control with
quantized light fields. We could also suggest potential application schemes for specific molecular species.
The computational techniques developed within the project have extended the quantum toolbox.
These new techniques now allow us to simulate molecular degrees of freedom on the same footing as
the quantized light field.
Moreover, we were able to lay important groundwork for future work on vibrational strong coupling.
We have developed a microscopic understanding of a broad variety of effects and how these effects do affect photochemical
reactions. We also have investigated various molecular species and estimated their controllability regarding control with
quantized light fields. We could also suggest potential application schemes for specific molecular species.
The computational techniques developed within the project have extended the quantum toolbox.
These new techniques now allow us to simulate molecular degrees of freedom on the same footing as
the quantized light field.
Moreover, we were able to lay important groundwork for future work on vibrational strong coupling.