Abstract
The development of efficient artificial leaves relies on the subtle combination of molecular assemblies able to absorb sunlight, converting light energy into electrochemical potential energy and finally transducing it into accessible chemical energy. The electronic design of these charge transfer molecular machines is crucial to build a complex supramolecular architecture for the light energy conversion. Here, we present an ab initio simulation of the whole decay pathways of a recently proposed artificial molecular reaction center. A complete structural and energetic characterization has been carried out with methods based on density functional theory, its time-dependent version, and a broken-symmetry approach. On the basis of our findings we provide a revision of the pathway only indirectly postulated from an experimental point of view, along with unprecedented and significant insights on the electronic and nuclear structure of intramolecular charge-separated states, which are fundamental for the application of this molecular assembly in photoelectrochemical cells. Importantly, we unravel the molecular driving forces of the various charge transfer steps, in particular those leading to the proton-coupled electron transfer final product, highlighting key elements for the future design strategies of such molecular assays.
Highlights
The development of efficient artificial leaves relies on the subtle combination of molecular assemblies able to absorb sunlight, converting light energy into electrochemical potential energy and transducing it into accessible chemical energy
The best inspiration for the design of such devices is definitely provided by nature that developed an extremely efficient molecular machine the photosystem II (PSII) able to convert sunlight into chemically accessible energy.[8−10,14]
PSII uses solar photons to drive the oxidation of water to dioxygen in an amazing way, combining different specialized molecular units.[14−16] this system is an optimum starting point for the construction of artificial photosynthetic machines
Summary
The development of efficient artificial leaves relies on the subtle combination of molecular assemblies able to absorb sunlight, converting light energy into electrochemical potential energy and transducing it into accessible chemical energy. This state is characterized by an electronic excitation completely localized on the TCNP unit.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.